Poly(acrylated polyol) and method for making and using thereof as asphalt rubber modifiers, adhesive, fracking additives, or fracking fluids

ABSTRACT

The present invention relates to a thermoplastic copolymer, block copolymer, and statistical copolymer comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups. The acrylated polyol monomeric units have an average degree of acrylation greater than 1 and less than the number of the hydroxyl groups of the polyol. The present invention also relates to a method of making the thermoplastic copolymer, block copolymer, and statistical copolymer, and using them in various applications, such as asphalt rubber modifiers, adhesives, or an additive in a fracking fluid for oil fracking.

This application is a divisional of U.S. patent application Ser. No.14/717,777, filed May 20, 2015, now U.S. Pat. No. 10,066,051, whichclaims the benefit of U.S. Provisional Patent Application Ser. No.62/001,444, filed May 21, 2014, which are hereby incorporated byreference in their entirety.

FIELD OF THE INVENTION

The present invention relates to a novel thermoplastic polymercomposition and methods of making and using thereof. In particular, thepresent invention relates to successful application of controlled freeradical polymerization on an acrylated polyol composition for makingnovel thermoplastic copolymers, block copolymers, and statisticalcopolymers, and using them in various applications such as asphaltrubber modifiers, adhesives, or additives in fracking fluids for thefracking industry.

BACKGROUND OF THE INVENTION

The global asphalt market is to reach 118.4 million metric tons by 2015,according to a January 2011 report by Global Industry Analysts, Inc. Theasphalt paving industry accounts for the largest end-use market segmentof asphalt. With increasing growth in the developing markets of China,India, and Eastern Europe, asphalt will be increasingly needed toconstruct roadway infrastructure for the next decade. The increaseddemand for asphalt, along with the need for improved asphaltmaterials/pavement performance, creates the opportunity for an asphaltmodifier.

The grade of the asphalt governs the performance of paving mixtures atin-service temperatures. In many cases, the characteristics of bitumenneeds to be altered to improve its elastic recovery/ductility at lowtemperatures for sufficient cracking resistance as well as to increaseits shearing resistance for sustained loads and/or at high temperaturesfor rutting resistance. Thus, to provide durable pavements, polymermodifiers are added to confer the desired physical properties to theasphalt. Typical polymer modifiers used include a suspendedsemicrystalline solid (e.g., polyethylene) or a dispersed SBS-typethermoplastic elastomer (e.g., various SBS products of the Kraton®family).

Over the past decade, there has been increased use of recycled tirerubber in asphalt binders as an alternative to polymer modifiers in theasphalt paving industry due to its good performance and competitiveeconomic opportunity. The use of ground tire rubber (GTR) as an asphaltmodifier is an environmentally sustainable mean of enhancing thepavement quality while recycling vast quantities of waste material.Asphalt rubber (AR) binders have being applied since the 1960s. However,the production and storage of the AR presents some challenges. It isimportant to have the rubber particles evenly distributed in the asphaltmatrix for the asphalt rubber. Because the rubber in the GTR iscrosslinked, it does not melt completely in asphalt at the blending andproduction temperatures commonly used. Thus, the AR binders requirehigher mix and compaction temperatures than the conventional binders.Also, the AR binders typically have some degree of separation duringstorage due to the immiscibility of the GTR with the asphalt and thedisparity in the specific gravities. To increase the asphalt rubber'sperformance and maintain the storage stability of the rubber after beingreacted in asphalt, stabilizers/compatibilizers have been commonly usedto swell the rubber particles and form either physical or chemicallinkages between the GTR filler particle and asphalt binder.

There are several stabilizers in the market for asphalt rubbers. Forexample, an additive widely used in the production of AR to reduce mixand compaction temperatures and to prevent separation is polyoctanamer(often referred to as Vestenamer®, Evonik Industries/Degussa). However,the conventional binders are expensive and do not provide environmentalbenefits. With the forecast of increasing demand of asphalt pavement andAR binders for the next decade, there remains a strong need for newtypes of cost-effective, environment-friendly, viable polymers that canbe used as AR binders in lieu of standard asphalt-rubber binders.

Adhesives are materials that can be fluid, semi-fluid, or materials thatcan become fluid with external assistance such as heating (e.g.,hot-melt adhesives). When applied between two objects, thesolidification of the adhesives stick the objects together. The adhesiveindustry is divided into the packaging industry with a 37% share of thetotal market, the construction industry with a 20% share (e.g., carpetlaying, roofing, pre-finished panels, etc.), the automobile industrywith a 19% share, the laminates industry with a 12% share (e.g.,labelling, veneers, laminates), the footwear industry with a 5% share,the consumer industry with a 4% share, and other markets constitutingthe remaining 3% share.

The global market for adhesives in 2013 was estimated by the Adhesiveand Sealant Council to be $40.5 billion in sales (approximately 9000kilo tons) and is expected to reach $58 billion in sales by 2018(approximately 12,400 kilo tons). There thus remains a strong need inthe art for new types of cost-effective, environment-friendly, viablepolymers that can be used as adhesives.

“Fracking”, or hydraulic fracturing, is a process for natural gas,petroleum, or uranium solution-extraction from deep formations of shale.The process involves the fracturing of shale rock deposits by apressurized liquid. The fracking liquid is a mixture of water, sand, andother chemical additives. The typical recipe for fracking fluidsconsists of 90% water, 8-9% sand, and 1-2% other chemicals such asbiocides, acids, inhibitors, stabilizers, crosslinkers, frictionreducers, pH adjusting agents, iron control, surfactants, and gellingagents. Because fracking can consume millions of gallons of frackingfluids, 1-2% of the fracking fluids (i.e., 1-2% chemicals among thefracking fluids) can still amount to hundreds of tons. This can be verytoxic for the soil and can attribute to deep water well contamination.There is thus a need in the art to develop a polymer as a substitute forthe gelling agents such as guar gum, that can serve as a thickeningagent for water, as a crosslinking agent, as a pH adjusting agent, as abreaking agent, and as a biocide.

Polymers based on glycerol have been used in the past decade in thefabrication of matrices for drug delivery, scaffolds in tissueengineering, plus many other applications. Similar chemistries have beenapplied to sorbitol to make polymers. For example, Liu et al,“Preparation and characterization of a thermoplastic poly(glycerolsebacate) elastomer by two-step method,” Journal of Applied PolymerScience 103(3):1412-19 (2007), synthesized a thermoplastic elastomerprepared using poly(glycerol-sebacate) and sebacic acid in a two-stepmethod. Cai et al., “Shape-memory effect of poly (glycerol-sebacate)elastomer,” Materials Letters 62(14):2171-73 (2008), were able tosynthesize a poly(glycerol-sebacate) elastomer with excellentshape-memory capabilities.

However, these past efforts have been focusing on acid/alcoholcondensation chemistry between glycerol or sorbitol monomer and anothermonomer. None of them have explored the biopolymers based onpolymerization of a polyol monomer or its derivatives. There is thus aneed in the art to use a monomer derived from an inexpensive naturalbiofeedstocks or petrochemical feedstocks to develop a highlyprocessable thermoplastic and elastomeric polymer with a wide range ofapplications and physical properties.

The present invention is directed to fulfilling these needs in the art.

SUMMARY OF THE INVENTION

One aspect of the present invention relates to a thermoplastic copolymercomprising plural acrylated polyol monomeric units having differentdegrees of acrylation of hydroxyl groups. The acrylated polyol monomericunits have an average degree of acrylation greater than 1 and less thanthe number of the hydroxyl groups of the polyol.

Another aspect of the invention relates to a thermoplastic blockcopolymer comprising at least one PA block and at least one PB block. PArepresents a polymer block comprising one or more units of monomer A andPB represents a polymer block comprising one or more units of monomer B.Monomer A is an acrylated polyol monomeric unit having different degreesof acrylation of hydroxyl groups. The acrylated polyol monomeric unithas an average degree of acrylation greater than 1 and less than thenumber of the hydroxyl groups of the polyol. Monomer B is a radicallypolymerizable monomer.

Another aspect of the invention relates to a thermoplastic statisticalcopolymer having a general formula of: [A_(i)-B_(h)—C_(k)]_(q). Arepresents monomer A, which is an acrylated polyol monomeric unit havingdifferent degrees of acrylation of hydroxyl groups. The acrylated polyolmonomeric unit has an average degree of acrylation greater than 1 andless than the number of the hydroxyl groups of the polyol. B representsmonomer B, which is a radically polymerizable monomer. C representsmonomer C, which is a radically polymerizable monomer. The monomer B isdifferent than the monomer A, and the monomer C is different than themonomer A or monomer B. i, j, and k are average number of repeatingunits of monomer A, monomer B, and monomer C, respectively, such that iand j are each greater than 0 and less than 1, k is 0 to less than 1,provided that i+j+k=1. q represents the number average degree ofpolymerization and ranges from 10 to 100,000.

These thermoplastic copolymers, block copolymers, and statisticalcopolymers can be partially or fully hydrophilic, and thus partially orfully water soluble, and can be partially or fully biodegradable.

One aspect of the present invention relates to a method of making athermoplastic copolymer or block copolymer. The method comprisesproviding an acrylated polyol composition comprising plural acrylatedpolyol monomeric units having different degrees of acrylation ofhydroxyl groups. The acrylated polyol composition has an average degreeof acrylation greater than 1 and less than the number of the hydroxylgroups of the polyol. The method also comprises polymerizing theacrylated polyol composition through controlled radical polymerizationto form the thermoplastic copolymer or block copolymer.

Another aspect of the invention relates to a method of preparing athermoplastic statistical copolymer. The method comprises providingmonomer A, which is an acrylated polyol monomeric unit having differentdegrees of acrylation of hydroxyl groups, wherein the acrylated polyolmonomeric unit has an average degree of acrylation greater than 1 andless than the number of the hydroxyl groups of the polyol. The methodalso comprises providing a radically polymerizable monomer, representedby B. The method further comprises polymerizing monomer A and monomer Bsimultaneously, via reversible addition-fragmentation chain-transferpolymerization (RAFT), in the presence of a free radical initiator and achain transfer agent to form the thermoplastic statistical copolymer.

Another aspect of the present invention relates to an asphaltcomposition. The asphalt composition comprises: i) an asphalt component;ii) a crumb rubber having a weight percentage in the range of 1% to 15%;and iii) a thermoplastic copolymer, block copolymer, or statisticalcopolymer as an asphalt additive, modifier, and/or filler having aweight percentage in the range of 0.01% to 1.05%.

Another aspect of the present invention relates to a method forpreparing a homogeneous asphalt composition. The method comprises mixinga thermoplastic copolymer, block copolymer, or statistical copolymer asan asphalt additive, modifier, and/or filler, with a weight percentagein the range of 0.01% to 1.05%, into an asphalt composition to form ahomogeneous asphalt composition. The asphalt composition comprises: i)an asphalt component, and ii) a crumb rubber having a weight percentagein the range of 1% to 15%.

Another aspect of the present invention relates to a method forpreparing an adhesive or sealant composition. The method comprisesmixing the thermoplastic copolymer, statistical copolymer, or blockcopolymer with a tackifier, and/or a plasticizer, and/or a solvent.

Another aspect of the present invention relates to a method forpreparing a fracking liquid. The method comprises mixing thethermoplastic copolymer, statistical copolymer, or block copolymer as achemical additive, with water, and sand.

For each of the above aspects of the asphalt composition, the method forpreparing a homogeneous asphalt composition, and the method forpreparing a fracking liquid, the thermoplastic copolymer, statisticalcopolymer, or block copolymer are discussed as below. The thermoplasticcopolymer comprises plural acrylated polyol monomeric units havingdifferent degrees of acrylation of hydroxyl groups. The acrylated polyolmonomeric units have an average degree of acrylation greater than 1 andless than the number of the hydroxyl groups of the polyol. Thethermoplastic statistical copolymer has a general formula of:[A_(i)-B_(j)—C_(k)]_(q). A represents monomer A, which is an acrylatedpolyol monomeric unit having different degrees of acrylation of hydroxylgroups. The acrylated polyol monomeric unit has an average degree ofacrylation greater than 1 and less than the number of the hydroxylgroups of the polyol. B represents monomer B, which is a radicallypolymerizable monomer. C represents monomer C, which is a radicallypolymerizable monomer. The monomer B is different than the monomer A,and the monomer C is different than the monomer A or monomer B. i, j,and k are average number of repeating units of monomer A, monomer B, andmonomer C, respectively, such that i and j are each greater than 0 andless than 1, k is 0 to less than 1, provided that i+j+k=1. q representsthe number average degree of polymerization and ranges from 10 to100,000. The thermoplastic block copolymer comprising at least one PAblock and at least one PB block. PA represents a polymer blockcomprising one or more units of monomer A and PB represents a polymerblock comprising one or more units of monomer B. Monomer A is anacrylated polyol monomeric unit having different degrees of acrylationof hydroxyl groups. The acrylated polyol monomeric unit has an averagedegree of acrylation greater than 1 and less than the number of thehydroxyl groups of the polyol. Monomer B is a radically polymerizablemonomer.

The present invention involves the successful application of controlledfree radical polymerization to multifunctional polyols, which can bederived from natural biofeedstocks or petrochemical feedstocks, e.g.,glycerol and sorbitol, yielding thermoplastic rubbers.

Glycerol (1,2,3-propanetriol) is typically derived from both natural andpetrochemical feedstocks (e.g., it is a co-product from the productionof biodiesel, via soybean oil and other feedstocks), and is consideredone of the most versatile chemicals for its wide range of applications.It is the backbone of all animal and vegetable triglycerides,constituting an average 10 wt % of the fatty portion. With the recentexplosion in production of biofuels, glycerol has rapidly become asurplus in the market, as it is created as a byproduct in themanufacturing of biodiesel by transesterification of vegetable oils withmethanol using NaOH as a catalyst (Pagliaro et al., “The Future ofGlycerol: 2nd Edition. RSC Green Chemistry,” (The Royal Society ofChemistry, 2^(nd) ed. 2010), which is herein incorporated by referencein its entirety). Sorbitol ((2S,3R,4R,5R)-hexane-1,2,3,4,5,6-hexol) iscommonly produced from corn syrup or other sources of biomass. Dextroseis a simple monosaccharide found in plants. These small polyolscurrently represent some of the most inexpensive commodity chemicalsavailable, ranging from $0.15 to $0.30 per pound. Thus, glycerol,sorbitol, and dextrose are “green,” inexpensive, and offer multiplefunctional sites that can be exploited to alter their properties to beincorporated into biobased polymers.

Polyols are converted by standard acid- or base-catalyzed condensationchemistry to contain the conjugated and readily polymerizable acrylic(C═O—C═C) moiety. The resulting acrylated polyol can be represented byAP_(x), in which x represents the average number of acrylic groups permolecule. At least one and as many as the maximum number of hydroxylfunctionalities in the polyol can be arylated. Controlled free radicalpolymerization techniques, such as atom transfer radical polymerization(ATRP) and reversible addition-fragmentation chain transferpolymerization (RAFT) can be applied to these acrylated polyol monomersto yield thermoplastic rubbers or elastomers.

The distinctive feature of this polymerization is that it allows thedesign of the molecular architecture of the resultant polymers such thatthey are predominantly non-crosslinked linear or lightly branched chainsthat behave as rubbers/elastomers at room temperature but reversiblymelt and are susceptible to common processing techniques at elevatedtemperatures. The success of the technology on polyols such as glycerol,sorbitol, or dextrose is surprising, as the multifunctional nature ofpolyol such as glycerol, sorbitol or dextrose have likely eliminatedthem as being considered as candidates for the basis of chain growthpolymerization chemistries—even AG₁ (acrylated glycerol having anaverage of one acrylic group per molecule) contains a significantfraction of di- and even tri-acrylated moieties. Thus, it is reasonablyexpected that it would be fairly difficult to polymerize these monomersto result in a high molar mass thermoplastic polymer without gelation.However, the inventors have discovered that under certain conditions,ATRP and RAFT polymerizations can be successfully applied to polymerizeacrylated polyols to achieve a high molecular weight and conversionrate.

The resulting acrylated polyol or poly(acrylated polyol) presentproperties capable of reducing mix and compaction temperatures, andpreventing separation of rubbers during AR storage. Thus, the acrylatedpolyol or poly(acrylated polyol), such as acrylated glycerol,poly(acrylated glycerol), acrylated sorbitol, and/or poly(acrylatedsorbitol), can be formulated as bio-based additives for the modificationof asphalt cements. Moreover, the inventors have discovered that certainspecific formulations of poly(acrylated polyols)—e.g., poly(acrylatedglycerol) or poly(acrylated sorbitol)—have excellent properties as ARmodifiers. For example, when added into an asphalt rubber composition,certain formulations of poly(acrylated polyols) can reduce mix andcompaction temperature in asphalt cements, and thus can be used as“warm-mix” additive properties; certain formulations of poly(acrylatedpolyols) can extend the service temperature, and thus can be used as“grade-range extender”; certain formulations of poly(acrylated polyols)can prevent separation during AR storage, and thus can be used as“stabilizer/compatibilizer”; and certain formulations of poly(acrylatedpolyols) can soften otherwise unworkable asphalts such as those fromvacuum tower bottoms, and thus can be used as “fluxes,” i.e., additivesused to soften asphalts from vacuum tower bottoms.

This technology enables the development of “green” and economicalalternatives to petrochemically derived thermoplastic polymers. Theresulting poly(acrylated polyol)-based thermoplastic copolymer can beused in thermoplastic rubber or elastomeric compositions for a varietyof applications, such as adhesives (e.g., pressure-sensitive adhesives,hot-melt adhesives, or water soluble adhesives), sealants, components oftires, shoes, consumer electronics, bitumen modifiers, or viscositymodifiers for consumer care products or the oil fracking industry.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the chemical structures for glycerol and sorbitol, andexemplary acrylated glycerol (AG_(x)) and exemplary acrylated sorbitol(AS_(x)) that may be present in the monomeric acrylated polyols, inwhich x is the number of acrylic groups. Acrylic groups were attached toglycerol or sorbitol through acid- or base-catalyzed condensation ofglycerol or sorbitol with acrylic acid.

FIG. 2A is a graph showing the results of ¹³C-NMR for glycerol usingdeuterated DMSO as the solvent. FIGS. 2B-2D are graphs showing theresults of ¹³C NMR for acrylated glycerol (AG) using deuterated DMSO asthe solvent. The sample in FIG. 2B shows 0.85 acrylic groups perglycerol molecule. The sample in FIG. 2C shows 0.91 acrylic groups perglycerol molecule. The sample in FIG. 2D shows 2.15 acrylic groups perglycerol molecule.

FIG. 3 is a graph showing the results of differential scanningcalorimetry (DSC) for a poly(acrylated glycerol) (“P(AG)”) samplesynthesized from the polymerization for 12 hours.

FIGS. 4A-4B are graphs showing the rheology curves of P(AG) samplessynthesized using two different chain transfer agents: EMP (FIG. 4A) andETMP (FIG. 4B), respectively. Reference temperature was 20° C.

FIG. 5 is a graph showing the result of proton ¹H-NMR for AG and P(AG).

FIG. 6 is a graph showing the results of DSC of a P(AG) sample (ghrmf82,see Table 3). A glass transition temperature is shown in the graph at−30° C.

FIGS. 7A-7B are graphs showing rheology curves for P(AG) samples with alow molecular weight (reference temperature was 50° C.) (FIG. 7A), and amedium molecular weight (reference temperature was 80° C.) (FIG. 7B).

FIGS. 8A-8C are graphs showing the viscosities results at varioustemperatures for the asphalt rubber (AR) binders and residual AR for thethree samples in Example 3, Experiment 1: control AR (FIG. 8A); AR-V(FIG. 8B); and AR-AG (FIG. 8C).

FIGS. 9A-9C are graphs showing the rheology results measured by DSR atvarious conditions (unaged, RTFO aged, and PAV aged) for the AR bindersand residual AR for the three samples in Example 3, Experiment 1:control AR (FIG. 9A); AR-V (FIG. 9B); and AR-AG (FIG. 9C).

FIGS. 10A-10C are graphs showing the grading results for the AR bindersand residual AR for the three samples in Example 3, Experiment 1:control AR; AR-V; and AR-AG. FIG. 10A presents the G*/sin δ results.FIG. 10B presents the G* results. FIG. 10C presents the δ results.

FIGS. 11A-11C are graphs showing the separation results for the ARbinders and residual AR for the three samples in Example 3, Experiment1: control AR (FIG. 11A); AR-V (FIG. 11B); and AR-AG (FIG. 11C).

FIGS. 12A-12C are graphs showing the viscosities results at varioustemperatures for the AR binders and residual AR for the oven-cured threesamples in Example 3, Experiment 2: control AR (FIG. 12A); AR-V (FIG.12B); and AR-AG (FIG. 12C).

FIGS. 13A-13C are graphs showing the rheology results measured by DSRfor the AR binders and residual AR for the oven-cured three samples inExample 3, Experiment 2: control AR (FIG. 13A); AR-V (FIG. 13B); andAR-AG (FIG. 13C).

FIGS. 14A-14C are graphs showing the separation results for the ARbinders and residual AR for the three samples in Example 3, Experiment2: control AR (FIG. 14A); AR-V (FIG. 14B); and AR-AG (FIG. 14C).

FIGS. 15A-15F are graphs showing the comparison results between thesamples in Experiment 1 and Experiment 2 in Example 3. FIG. 15A comparesthe grading results (G*/sin δ) for the AR binders and residual AR. FIG.15B compares the grading results (G*) for the AR binders and residualAR. FIG. 15C compares the grading results (δ) for the AR binders andresidual AR. FIG. 15D-15F compares the viscosities results for the ARbinders and residual AR for control AR (FIG. 15D), AR-V (FIG. 15E), andAR-AG (FIG. 15F), respectively.

FIG. 16 shows tables and graphs summarizing the high temperaturecontinuous grade for the unaged AR binders modified by P(AG), comparedto the results of a non-stabilized AR (control), AR binders stabilizedwith Vestenamer®, and an asphalt binder modified with 5% Kraton®.

FIG. 17 shows tables and graphs summarizing the high temperaturecontinuous grade for the RTFO-aged AR binders modified by P(AG),compared to the results of a non-stablized AR (control), AR bindersstabilized with Vestenamer®, and an asphalt binder modified with 5%Kraton®.

FIG. 18 shows tables and graphs summarizing the mass loss percentageduring the RTFO testing of the residual binder.

FIG. 19 shows tables and graphs summarizing the intermediate temperaturecontinuous grade for the RTFO+PAV aged AR binders modified by P(AG),compared to the results of a non-stablized AR (control), AR bindersstabilized with Vestenamer®, and an asphalt binder modified with 5%Kraton®.

FIG. 20 shows tables and graphs summarizing the low temperaturecontinuous grade for the RTFO+PAV-aged AR binders modified by P(AG),compared to the results of a non-stablized AR (control), AR bindersstabilized with Vestenamer®, and an asphalt binder modified with 5%Kraton®.

FIG. 21A is a graph showing the results of viscosities for the ARbinders modified by P(AG), compared to the results of a non-stablized AR(control), and the AR binders stabilized with Vestenamer®. Theviscosities were measured at 20 rpm. FIG. 21B is a graph showing theresults of viscosities for the residual AR binders measured at 20 rpm.

FIG. 22 shows tables and graphs summarizing the percentage difference inDSR storage stability for AR binders modified by P(AG), compared to theresults of a non-stablized AR (control), AR binders stabilized withVestenamer®, and an asphalt binder modified with 5% Kraton®.

FIG. 23 shows tables and graphs summarizing the grade range for ARbinders modified by P(AG), compared to the results of a non-stablized AR(control), AR binders stabilized with Vestenamer®, and an asphalt bindermodified with 5% Kraton®.

FIG. 24 shows tables and graphs summarizing the minimum mixingtemperatures for AR binders modified by P(AG), compared to the resultsof a non-stabilized AR (control), AR binders stabilized withVestenamer®, and an asphalt binder modified with 5% Kraton®.

FIG. 25 shows tables and graphs summarizing the minimum compactiontemperatures for AR binders modified by P(AG), compared to the resultsof a non-stabilized AR (control), AR binders stabilized withVestenamer®, and an asphalt binder modified with 5% Kraton®.

FIG. 26 shows tables and figures summarizing the average differencebetween AR and residual viscosities for AR binders modified by P(AG),compared to the results of a non-stablized AR (control), AR bindersstabilized with Vestenamer®, and an asphalt binder modified with 5%Kraton®.

FIG. 27 shows tables and graphs summarizing the final percentage ratingof the AR binders stabilized with P(AG) and Vestenamer®, analyzedagainst the control AR (non-stabilized).

FIG. 28 shows tables and graphs summarizing the final percentage ratingof the AR binders stabilized with P(AG), analyzed against the ARmodified with Vestenamer®.

FIG. 29 is a graph showing the results of gel permeation chromatographytraces of three poly(acrylated glycerol) (“PAG”) polymers havingmolecular weights ranging from 1 million Daltons to 10 thousand Daltons.

FIGS. 30A-C show the images of the poly(acrylated glycerol) polymer withmolecular weight of 10K Daltons (FIG. 30A), 100K Daltons (FIG. 30B), and1 million Daltons (FIG. 30C).

DETAILED DESCRIPTION OF THE INVENTION

One aspect of the present invention relates to a thermoplastic copolymercomprising plural acrylated polyol monomeric units having differentdegrees of acrylation of hydroxyl groups. The acrylated polyol monomericunits have an average degree of acrylation greater than 1 and less thanthe number of the hydroxyl groups of the polyol.

Another aspect of the invention relates to a thermoplastic blockcopolymer comprising at least one PA block and at least one PB block. PArepresents a polymer block comprising one or more units of monomer A andPB represents a polymer block comprising one or more units of monomer B.Monomer A is an acrylated polyol monomeric unit having different degreesof acrylation of hydroxyl groups. The acrylated polyol monomeric unithas an average degree of acrylation greater than 1 and less than thenumber of the hydroxyl groups of the polyol. Monomer B is a radicallypolymerizable monomer.

Another aspect of the invention relates to a thermoplastic statisticalcopolymer having a general formula of: [A_(i)-B_(j)—C_(k)]_(q). Arepresents monomer A, which is an acrylated polyol monomeric unit havingdifferent degrees of acrylation of hydroxyl groups. The acrylated polyolmonomeric unit has an average degree of acrylation greater than 1 andless than the number of the hydroxyl groups of the polyol. B representsmonomer B, which is a radically polymerizable monomer. C representsmonomer C, which is a radically polymerizable monomer. The monomer B isdifferent than the monomer A, and the monomer C is different than themonomer A or monomer B. i, j, and k are average number of repeatingunits of monomer A, monomer B, and monomer C, respectively, such that iand j are each greater than 0 and less than 1, k is 0 to less than 1,provided that i+j+k=1. q represents the number average degree ofpolymerization and ranges from 10 to 100,000.

The polyols that can be used in the thermoplastic copolymer, blockcopolymer, or statistical copolymer include any polyols that are readilyderived from natural biofeedstock or petrochemical feedstock as well assaccharides that contain multiple hydroxyl functional groups. Suitablepolyols include, but are not limited to, ethylene glycol, propyleneglycol, dipropylene glycol, 1,2,4-butanetriol, 1,7-heptanediol,glycerol, panaxatriol, panaxytriol, talose, balsaminol B, momordol,erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol,galactitol, isomalt, maltitol, and mixtures thereof. Suitable polyolscan also include saccharides such as aldohexose, aldopentose,aldotetrose, aldotriose, aldose, allose, altrose, arabinose,amylopectin, amylose, dextrose, erythrose, fructose, galactose, glucose,gulose, hexose, idose, ketohexose, ketose, lactose, lyxose, maltose,mannose, pentose, ribose, saccharose, sucrose, talose, tetrose, triose,xylose, as well as their respective stereoisomers. Exemplary polyolsused are glycerol, sorbitol, and dextrose.

The acrylated polyol monomeric unit can be represented by AG_(x), inwhich x represents the average number of acrylic groups per arylatedpolyol molecule. At least one and as many as the maximum number of thehydroxyl functionalities in the polyol molecule can be arylated in theacrylated polyol monomeric unit. For example, glycerol contains 3hydroxyl groups, and thus, in the acrylated glycerol represented byAG_(x), x can range from greater than 0 to 3. Likewise, sorbitolcontains 6 hydroxyl groups, and thus, in the acrylated sorbitolrepresented by AS_(x), x can range from greater than 0 to 6. In themonomeric acrylated polyol AP_(x), there can be a mixture of variousacrylated polyol with different degrees of acrylation. For example, inthe case of acrylated glycerol, while the majority monomeric acrylatedpolyol unit of AG₁ may be mono-acrylated glycerol, there can also besmall populations of acrylated polyol monomeric unit that arenon-acylated glycerol and di-acrylated glycerol (i.e., 2 hydroxyl groupsof glycerol are acrylated) as well. Moreover, the monomeric AP_(x) canalso possess a small number of oligomers of arylated polyols, as theautopolymerization of the acrylic groups may not be completelysuppressed. Accordingly, while AP_(x) is referred to as “monomers”herein, it is to be understood that these monomeric units can containmixtures having a distributions of various degree of arcylation andvarious molecular weight. Because the acrylated polyol monomeric unit isa mixture of various acrylated polyols, the resulting thermoplasticpolymer is considered as a copolymer.

Exemplary acrylated polyol monomeric units are acrylated glycerol,acrylated sorbitol, and acrylated dextrose. The average degree ofacrylation in acrylated glycerol can range from 0.01 to 3. Typically,the average degree of acrylation in acrylated glycerol ranges from 1.001to 2.9, for instance, from 1.001 to 1.25. The average degree ofacrylation in acrylated sorbitol can range from 0.01 to 6. Typically,the average degree of acrylation in acrylated sorbitol ranges from 1.001to 3. The average degree of acrylation in acrylated dextrose can rangefrom 0.01 to 5. Typically, the average degree of acrylation in acrylateddextrose ranges from 1.001 to 3. Structures of glycerol, sorbitol, andexemplary monomeric acrylated glycerol and acrylated sorbitol withdifferent degrees of acrylation are shown in FIG. 1.

The structure of an exemplary poly(acrylated glycerol) molecule is shownin Scheme 1. Scheme 1 shows that the copolymer is a mixture of X unitsof mono-acrylated glycerol, Y units of di-acrylated glycerol, and Zunits of tri-acrylated glycerol, and the resulting x, the average degreeof acrylation of the poly(acrylated glycerol) molecule can betheoretically calculated as (X+Y+Z)/3.

The thermoplastic copolymer has a linear or branched-chain structure,and has properties characteristic of thermoplastic substances in that ithas the stability necessary for processing at elevated temperatures andyet possesses good strength below the temperature at which it softens.The thermoplastic copolymer has a glass transition temperature (T_(g))below 0° C., for instance, from −60° C. to 0° C., from −60° C. to −15°C., or from −45° C. to −20° C. The thermoplastic copolymer has amolecular weight of at least 1 KDa, for instance, a molecular weight of1 KDa to 10 MDa, 10 KDa to 1 MDa, 50 KDa to 10 MDa, or 50 KDa to 200KDa.

The acrylated polyol monomeric unit can contain one or more conjugatedsites that can increase the reactivity of acrylated polyol towardspropagation reactions in the controlled radical polymerization.

In the thermoplastic block copolymer, the PA block represents a polymerblock comprising one or more units of monomer A, with monomer A being anacrylated polyol monomeric unit having different degrees of acrylationof hydroxyl groups, wherein the acrylated polyol monomeric unit has anaverage degree of acrylation greater than 1 and less than the number ofthe hydroxyl groups of the polyol. Monomer A has been discussed in theabove embodiments in the acrylated polyol-based thermoplastic copolymer.

The PB block can be polymerized from one or more radically polymerizablemonomers, which can include a variety type of monomers such as vinyl(such as vinyl aromatic), acrylic (such as methacrylates, acrylates,methacrylamides, acrylamides, etc.), diolefin, nitrile, dinitrile,acrylonitrile monomer, a monomer with reactive functionality, and acrosslinking monomer.

Vinyl aromatic monomers are exemplary vinyl monomers that can be used inthe block copolymer, and include any vinyl aromatics optionally havingone or more substituents on the aromatic moiety. The aromatic moiety canbe either mono- or polycyclic. Exemplary vinyl aromatic monomers for thePB block include styrene, α-methyl styrene, t-butyl styrene, vinylxylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, N-vinylheteroaromatics (such as 4-vinylimidazole (Vim), N-vinylcarbazole (NVC),N-vinylpyrrolidone, etc.). Other exemplary vinyls include vinyl esters(such as vinyl acetate (VAc), vinyl butyrate (VB), vinyl benzoate(VBz)), N-vinyl amides and imides (such as N-vinylcaprolactam (NVCL),N-vinylpyrrolidone (NVP), N-vinylphthalimide (NVPI), etc.),vinylsulfonates (such as 1-butyl ethenesulfonate (BES), neopentylethenesulfonate (NES), etc.), vinylphosphonic acid (VPA), haloolefins(such as vinylidene fluoride (VF2)), etc. Exemplary methacrylatesinclude C₁-C₆ (meth)acrylate (i.e., methyl methacrylate, ethylmethacrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutylmethacrylate, heptyl (meth)acrylate, or hexyl (meth)acrylate),2-(acetoacetoxy)ethyl methacrylate (AAEMA), 2-aminoethyl methacrylate(hydrochloride) (AEMA), allyl methacrylate (AMA), cholesterylmethacrylate (CMA), t-butyldimethylsilyl methacrylate (BDSMA),(diethylene glycol monomethyl ether) methacrylate (DEGMA),2-(dimethylamino)ethyl methacrylate (DMAEMA), (ethylene glycolmonomethyl ether) methacrylate (EGMA), 2-hydroxyethyl methacrylate(HEMA), dodecyl methacrylate (LMA), methacryloyloxyethylphosphorylcholine (MPC), (poly(ethylene glycol) monomethyl ether)methacrylate (PEGMA), pentafluorophenyl methacrylate (PFPMA),2-(trimethylamonium)ethyl methacrylate (TMAEMA),3-(trimethylamonium)propyl methacrylate (TMAPMA), triphenylmethylmethacrylate (TPMMA), etc. Other exemplary acrylates include2-(acryloyloxy)ethyl phosphate (AEP), butyl acrylate (BA),3-chloropropyl acrylate (CPA), dodecyl acrylate (DA), di(ethyleneglycol) 2-ethylhexyl ether acrylate (DEHEA), 2-(dimethylamino)ethylacrylate (DMAEA), ethyl acrylate (EA), ethyl a-acetoxyacrylate (EAA),ethoxyethyl acrylate (EEA), 2-ethylhexyl acrylate (EHA), isobornylacrylate (iBoA), methyl acrylate (MA), propargyl acrylate (PA),(poly(ethylene glycol) monomethyl ether) acrylate (PEGA), tert-butylacrylate (tBA), etc. Exemplary methacrylamides includeN-(2-aminoethyl)methacrylamide (hydrochloride) (AEMAm) andN-(3-aminopropyl)methacrylamide (hydrochloride) (APMAm),N-(2-(dimethylamino)ethyl)acrylamide (DEAPMAm),N-(3-(dimethylamino)propyl)methacrylamide (hydrochloride) (DMAPMAm),etc. Other exemplary acrylamides include acrylamide (Am)2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS),N-benzylacrylamide (BzAm), N-cyclohexylacrylamide (CHAm), diacetoneacrylamide (N-(1,1-dimethyl-3-oxobutyl) acrylamide) (DAAm),N,N-diethylacrylamide (DEAm), N,N-dimethylacrylamide (DMAm),N-(2-(dimethylamino)ethyl)acrylamide (DMAEAm), N-isopropylacrylamide(NIPAm), N-octylacrylamide (OAm), etc. Exemplary nitriles includeacrylonitrile, adiponitrile, methacrylonitrile, etc. Exemplary diolefinsinclude butadiene, isoprene, etc.

The radically polymerizable monomers suitable for usage herein alsoinclude those monomers with reactive functionality, e.g., a ‘clickable’functionality so that when the monomers are incorporated in blocks,these ‘clickable’ functional groups can be used as a precursor to apolymer brush or copolymerized to provide sites for the attachment offunctionality or for crosslinking. Exemplary reactive functionalityinclude functional groups suitable for azide-alkyne 1,3-dipolarcycloaddition, such as azide functionality; “active ester’ functionalgroups that are particular active with primary amine functionality;functional groups with protected thiol, hydrazide or aminofunctionality; functional groups with isocyanate or isothiocyanatefunctionality, etc.

The radically polymerizable monomers suitable for usage herein can alsoinclude those crosslinking monomers that are typically used both in thesynthesis of microgels and polymer networks (see below). The monomerscan include degradable crosslinks such as an acetal linkage, ordisulfide linkages, resulting in the formation of degradable crosslinks.Exemplary crosslinking monomers diethyleneglycol dimethacrylate(DEGDMA), triethylene glycol dimethacrylate (TEGDMA), ethyleneglycoldimethacrylate (EGDMA), hexane-1,6-diol diacrylate (HDDA),methylene-bis-acrylamide (MBAm), divinylbenzene (DVB), etc.

A more extensive list of exemplary methacrylate monomers, acrylatemonomers, methacrylamide monomers, acrylamide monomers, styrenicmonomers, diene monomers, vinyl monomers, monomers with reactivefunctionality, and crosslinking monomers that are suitable for usage asthe radically polymerizable monomers herein has been described in Moadet al., “Living Radical Polymerization by the Raft Process—a ThirdUpdate,” Australian Journal of Chemistry 65: 985-1076 (2012), which ishereby incorporated by reference in its entirety.

Moreover, two or more different monomers can be used together in theformation of the PB block or different PB block in the block copolymer.A typical radically polymerizable monomer B used herein is styrene, andthe resulting PB block is a styrene homopolymer. Another typicalradically polymerizable monomer B used herein is methyl acrylate, andthe resulting PB block is a methyl acrylate homopolymer.

The PB block can also be polymerized from one or more monomerictriglycerides, typically derived from a plant oil, animal fat, or asynthetic triglyceride. This polymerized plant oil or animal oil can besubsequently partially or fully saturated via a catalytic hydrogenationpost-polymerization. The monomeric oils used in the block copolymer canbe any triglycerides or triglyceride mixtures that are radicallypolymerizable. These triglycerides or triglyceride mixtures aretypically plant oils. Suitable plant oils include, but are not limitedto, a variety of vegetable oils such as soybean oil, peanut oil, walnutoil, palm oil, palm kernel oil, sesame oil, sunflower oil, saffloweroil, rapeseed oil, linseed oil, flax seed oil, colza oil, coconut oil,corn oil, cottonseed oil, olive oil, castor oil, false flax oil, hempoil, mustard oil, radish oil, ramtil oil, rice bran oil, salicornia oil,tigernut oil, tung oil, etc., and mixtures thereof. Typical vegetableoil used herein includes soybean oil, linseed oil, corn oil, flax seedoil, or rapeseed oil, and the resulting PB block is polymerizedtriglyceride or triglyceride derivatives.

The thermoplastic block copolymer can further comprise at least one PCblock. The PC block can be polymerized from one or more radicallypolymerizable monomers. Any monomer that is suitable to form the PBblock can be used to form the PC block.

The structure of an exemplary poly(acrylated glycerol) block copolymeris shown in Scheme 2. Scheme 2 shows that the copolymer is a mixture ofX units of mono-acrylated glycerol, Y units of di-acrylated glycerol, Zunits of tri-acrylated glycerol, and the resulting x, the average degreeof acrylation of the poly(acrylated glycerol) molecule can betheoretically calculated as (X+Y+Z)/3. R₁ and R₂ are polymer blocks(e.g., the PB block and the PC block, respectively), different from thepoly(acrylated glycerol) block.

The thermoplastic block copolymer has a molecular weight ranging from 5to 10 MDa, for instance, from 5 to 500 kDa, from about 15 to 300 kDa,from about 40 to about 100 kDa, or from about 80 to about 100 kDa. ThePA block has a glass transition temperature (T_(g)) below 0° C., orbelow −15° C., for instance, from −60° C. to 0° C., from −60° C. to −15°C., or from −45° C. to −20° C. Typically, the PA block, PB block, and PCblock, if present, each have a linear or branched-chain structure.

In the thermoplastic statistical copolymer [A_(i)-B_(j)—C_(k)]_(q),Monomer A is based on an acrylated polyol monomeric unit havingdifferent degrees of acrylation of hydroxyl groups. Monomer A has beendiscussed in the above embodiments in the acrylated polyol-basedthermoplastic copolymer.

Monomer B or monomer C can be each independently a vinyl, acrylic,diolefin, nitrile, dinitrile, acrylonitrile monomer, or monomer withreactive functionality, or crosslinking monomer. The exemplaryembodiments for monomer B and monomer C suitable for usage in thethermoplastic statistical copolymer are the same as the exemplaryembodiments for the monomer B, as described above in the thermoplasticblock copolymer. Exemplary monomer B and monomer C include styrene,α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene,vinyl pyridine, divinyl benzene, vinyl acetate, N-vinylpyrrolidone,methyl acrylate, C₁-C₆ (meth)acrylate (i.e., methyl methacrylate, ethylmethacrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl(meth)acrylate, or hexyl (meth)acrylate), acrylonitrile, adiponitrile,methacrylonitrile, butadiene, isoprene, radically polymerizable plantoils, or mixtures thereof. For example, the monomer B and the monomer Care each independently a vinyl aromatic monomer, such as a styrene; anacrylate monomer, such as a methyl (meth)acrylate; or a radicallypolymerizable plant oil, such as soybean oil, linseed oil, corn oil,flax seed oil, or rapeseed oil.

In one embodiment, the monomer C is absent.

One or more acrylated polyol monomeric units in the thermoplasticcopolymer, block copolymer, or statistical copolymer can also containone or more alkoxy groups, which can be derived from esterification ofthe un-acrylated hydroxy groups in the acrylated polyol. For instance,one or more acrylated polyol monomeric units in the thermoplasticcopolymer contain one or more methoxy or ethoxy groups.

Exemplary applications of the poly(acrylated polyol)-based thermoplasticcopolymers, block copolymers, and statistical copolymers include theiruse as “green” and economical alternatives to petrochemically derivedthermoplastic polymers. For example, the thermoplastic copolymers, blockcopolymers, or statistical copolymers can be used as rubbers orelastomers; as components in consumer electronics, such as component forshock/impact protection or cover components; as asphalt modifiers; asresin modifiers; as engineering resins; as leather and cement modifiers;in footwear, such as in rubber shoe heels, rubber shoe soles; inautomobiles, such as in tires, hoses, power belts, conveyor belts,printing rolls, rubber wringers, automobile floor mats, mud flaps fortrucks, ball mill liners, and weather strips; as sealants or adhesives(such as pressure sensitive adhesives, hot-melt adhesives, or watersoluble adhesives); in aerospace equipment; as viscosity modifiers forconsumer care products, such as viscosity index improvers; asdetergents; as diagnostic agents and supports therefore; as dispersants;as emulsifiers; as lubricants and/or surfactants; as paper additives andcoating agents; as additives for the fracking industry, as frackingfluid; and in packaging, such as food and beverage packaging materials.

In some embodiments, the poly(acrylated polyol)-based thermoplasticcopolymers, block copolymers, and statistical copolymers can be used asa main component in a thermoplastic elastomer composition, to improvethe thermoplastic and elastic properties of the composition. To form anelastomeric composition, the poly(acrylated polyol)-based thermoplasticcopolymers, block copolymers, or statistical copolymers can be furthervulcanized, cross-linked, compatibilized, and/or compounded with one ormore other materials, such as other elastomer, additive, modifier and/orfiller. The resulting elastomer can be used as a rubber composition, invarious industries such as in footwear, automobiles, packaging, or as anadditive in the fracking industry, etc.

In one embodiment, the poly(acrylated polyol)-based thermoplasticcopolymers, block copolymers, or statistical copolymers can be used inan automobile, such as in vehicle tires, hoses, power belts, conveyorbelts, printing rolls, rubber wringers, automobile floor mats, mud flapsfor trucks, ball mill liners, and weather strips. The automobilecomposition (e.g., vehicle tires) may further comprise a rubbercompound. The thermoplastic copolymers, block copolymers, or statisticalcopolymers can serve as a main component in a thermoplastic composition,to improve the thermoplastic and elastic properties of the automobilecompositions. The resulting compositions can be further vulcanized,cross-linked, compatibilized, and/or compounded with one or more othermaterials, such as other elastomer, additive, modifier and/or filler.

In one embodiment, the poly(acrylated polyol)-based thermoplasticcopolymers, block copolymers, or statistical copolymers can be used inan asphalt binder composition, as an asphalt additive, modifier and/orfiller. The asphalt binder composition may further comprise a crumbrubber.

In one embodiment, the poly(acrylated polyol)-based thermoplasticcopolymers, block copolymers, or statistical copolymers can be used inan adhesive or sealant composition. The adhesive or sealant compositionmay further comprise a tackifier and/or a plasticizer, and/or a solvent.Suitable solvents include, but are not limited to, water, and an organicsolvent such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF),benzene, dioxane, toluene, chloroform, hexane, cyclohexane, xylene,carbon tetrachloride, acetone, acetonitrile, butanol, heptane, andethanol. Suitable tackifiers include, but are not limited to,isosorbide-based tackifiers; Piccotac™1095 and Piccotac™8095; glycerolester tackifiers, such as Staybelite™ Ester 10-E Ester of HydrogenatedRosin and Staybelite™ Ester 3-E Ester of Hydrogenated Resin; Floral™AX-E Fully Hydrogenated Rosin; phenolic resins; styrenated terpenes;polyterpenes; rosin esters; terpene phenolics; and monomeric resins.Suitable plasticizers include, but are not limited to, benzoflex 2088(DEGD); abietic acid; Eastman™ Triacetin; Eastman 168™ non-phthalateplasticizer; polyalkylene esthers, such as polyethylene glycol,polytetramethylene glycol, polypropylene glycol, and mixtures thereof;glyceryl monostearate; octyl epoxy soyate, epoxidized soybean oil, epoxytallate, and epoxidized linseed oil; polyhydroxyalkanoate; glycols, suchas thylene glycol, pentamethylene glycol, and hexamethylene glycol;anionic or cationic plasticizers, such as dioctyl sulfosuccinate, alkanesulfonate, and sulfonated fatty acid; phthalate or trimellitateplasticizers; polyethylene glycol di-(2-ethylhexoate); citrate esters;naphthenic oil and dioctyl phthalate; white oil; lauric, sebacic, orcitric acids esters; nonfugitive polyoxyethylene aryl ether; copolymerof ethylene and carbon monoxide; photopolymerizable unsaturated liquidplasticizer; and sorbitol.

In one embodiment, the poly(acrylated polyol)-based thermoplasticcopolymers, block copolymers, or statistical copolymers can be used asan additive in the fracking fluid or as a fracking fluid. The frackingfluid may further comprise water and sand. A typical recipe for afracking fluid comprises about 90% water, about 8-9% sand, and about1-2% other chemicals such as biocides, acids, inhibitors, stabilizers,crosslinkers, friction reducers, pH adjusting agents, iron control,surfactants, and gelling agents. The poly(acrylated polyol)-basedthermoplastic copolymers, block copolymers, or statistical copolymerscan be used as a substitute for the gelling agents such as guar gum, canserve as a thickening agent for water, as a crosslinking agent, as a pHadjusting agent, as a breaking agent, or as a biocide. The frackingfluid composition can also comprise a thermoplastic polymer block addedto confer a desired fluid property to the thermoplastic copolymer,statistical copolymer, or block copolymer. Suitable thermoplasticpolymer block that can be added to the poly(acrylated polyol)-basedthermoplastic copolymers, block copolymers, or statistical copolymers,discussed in the above embodiments, can also be used herein.

Another aspect of the present invention relates to a method of making athermoplastic copolymer or block copolymer. The method comprisesproviding an acrylated polyol composition comprising plural acrylatedpolyol monomeric units having different degrees of acrylation ofhydroxyl groups. The acrylated polyol composition has an average degreeof acrylation greater than 1 and less than the number of the hydroxylgroups of the polyol. The method also comprises polymerizing theacrylated polyol composition through controlled radical polymerizationto form the thermoplastic copolymer or block copolymer.

An acrylated polyol composition can be prepared by reacting one or morepolyols with an acrylic reagent. Polyols are acrylated through astandard acid- or base-catalyzed condensation reaction. This reactiontypically occurs at a mild temperature and produces water as thenon-recyclable waste product. The reaction imparts acrylic functionalityto the polyol molecule, rendering it to be readily polymerized and tointeract with other rubber-like polymers such as polymers havingbackbones that contain tire rubber.

The acrylic reagent used can be an unsaturated carboxylic acid or anacidic halide. Suitable acrylic reagents include, but are not limitedto, acrylic acid, acryloyl chloride, methacrylic acid, or other acid oracidic halide terminated with a vinyl.

The acrylic reagent is typically added in excess of the polyol. Theamount of the acrylic reagent added may depend upon the desirable degreeof acrylation: the more excessive of the acrylic reagent relative to thepolyol, the larger degree of acrylation will be achieved. Typically, thestoichiometric ratio of the acrylic reagent to the polyol can range from1 to the maximum number of the hydroxyl functionalities in the polyolmolecule. For instance, the stoichiometric ratio of the acrylic reagentto glycerol typically ranges from 1 to 3.

The acrylation reaction is typically carried out at a temperature of 30°C. to 130° C., at a temperature of 50° C. to 110° C., or at atemperature of 90° C. to 110° C. The acrylation reaction can be carriedout in the presence of a catalyst. Suitable catalysts include, but arenot limited to, a homogeneous catalyst such as triphenyl phosphine ortriamine pyrophosphate, or a heterogeneous polyanionic resin, such asthe Amberlyst™ family (e.g., amberlyst 15). The acrylation reaction canbe carried out in the presence of an inhibitor. Exemplary inhibitorsinclude, but are not limited to, phenothiazine, hydroquinone, orantioxidant inhibitors such as the ETHANOX family (e.g., ETHANOX 330™.

The resulting arylated polyol can be represented by AP_(x), in which xrepresents the average number of acrylic groups per arylated polyolmolecule. At least one and as many as the maximum number of the hydroxylfunctionalities in the polyol molecule can be arylated. For example,glycerol contains 3 hydroxyl groups prior to being acrylated. Acrylationof glycerol results AG_(x), x can range from greater than 0 to 3.Likewise, sorbitol contains 6 hydroxyl groups prior to being acrylated.Acrylation of sorbitol results AS_(x), where x ranges from greater than0 to 6. In the resulting arylated polyol, AP_(x), there can be adistribution of all possible reaction products. For example, in the caseof acrylated glycerol, while AG₁ may be composed of mostly mono-acylatedglycerol, there can also be small populations of non-acylated glyceroland di-acrylated glycerol as well.

Moreover, autopolymerization of the acrylic groups may not be completelysuppressed. Thus, AP_(x) can also possess a small number of oligomers ofarylated polyol. Accordingly, while AP_(x) is referred to as “monomers”herein, it is to be understood that these monomeric units can containmixtures having a distributions of various degree of arcylation andvarious molecular weight.

Suitable polyols for acrylation include, but are not limited to,ethylene glycol, propylene glycol, dipropylene glycol,1,2,4-butanetriol, 1,7-heptanediol, glycerol, panaxatriol, panaxytriol,talose, balsaminol B, momordol, erythritol, enterodiol, xylitol,miglitol, sorbitol, mannitol, galactitol, isomalt, and maltitol.Suitable polyols can also include saccharides such as aldohexose,aldopentose, aldotetrose, aldotriose, aldose, allose, altrose,arabinose, amylopectin, amylose, dextrose, erythrose, fructose,galactose, glucose, gulose, hexose, idose, ketohexose, ketose, lactose,lyxose, maltose, mannose, pentose, ribose, saccharose, sucrose, talose,tetrose, triose, xylose, as well as their respective stereoisomers.Exemplary polyols used are glycerol, sorbitol, and dextrose. The averagedegree of acrylation for glycerol can range from 0.01 to 3. Typically,the average degree of acrylation for glycerol ranges from 1.001 to 2.9,for instance, from 1.001 to 1.25. The average degree of acrylation forsorbitol can range from 0.01 to 6. Typically, the average degree ofacrylation for sorbitol ranges from 1.001 to 3.

The acrylated polyol composition can then be polymerized through, e.g.,free radical, anionic, or controlled radical polymerization. Typically,controlled radical polymerization is conducted on the acrylated polyolcomposition to form a thermoplastic copolymer, block copolymer, orstatistical copolymer. The polymerizing step is carried out underconditions effective to produce the thermoplastic copolymer, blockcopolymer, or statistical copolymer with a molecular weight of at least1 KDa without gelation. The resulting thermoplastic copolymer, blockcopolymer, or statistical copolymer has a linear or branched-chainstructure.

The side reactions in the acrylation process can promote the joining ofmono-acrylated polyol, di-acrylated polyol, or other multi-acrylatedpolyol to form larger molecules known as oligomers. The acrylatedglycerol monomer or oligomers may be further polymerized.

The polymerizing step is performed through living free radicalpolymerization which involves living/controlled polymerization with freeradical as the active polymer chain end (Moad et al., “The Chemistry ofRadical Polymerization—Second Fully Revised Edition,” Elsevier ScienceLtd. (2006), which is hereby incorporated by reference in its entirety).This form of polymerization is a form of addition polymerization wherethe ability of a growing polymer chain to terminate has been removed.The rate of chain initiation is thus much larger than the rate of chainpropagation. The result is that the polymer chains grow at a moreconstant rate than seen in traditional chain polymerization and theirlengths remain very similar. The polymerizing step typically occurs inthe presence of a free radical initiator, and a catalyst or a chaintransfer agent to form the thermoplastic copolymer.

One form of living free radical polymerization is atom transfer radicalpolymerization. Atom transfer radical polymerization (ATRP) is acatalyzed, reversible redox process that achieves controlledpolymerization via facile transfer of labile radicals (e.g., halideradicals) between growing polymer chains and a catalyst (Davis et al.,“Atom Transfer Radical Polymerization of tert-Butyl Acrylate andPreparation of Block Copolymers,” Macromolecules 33:4039-4047 (2000);Matyjaszewski et al., “Atom Transfer Radical Polymerization,” ChemicalReviews 101:2921-2990 (2001), which are hereby incorporated by referencein their entirety). In ATRP, chain termination and transfer reactionsare essentially eliminated by keeping the free radical concentrationsmall. Briefly, the mechanism by which ATRP operates may be summarizedas:P−X+Cu_(I)X

P.+Cu_(II)X₂  (1)P₁.+M

P_(i+1).  (2)

In Equation (1), the labile radical X may be a halogen (e.g., Br, Cl)attached to end of a polymer P. The catalyst, Cu_(I)Br, reversiblyabstracts this halogen, forming a polymer free radical (P.). Theequilibrium achieved between inert polymers and active polymer freeradicals strongly favors the left side (K<<10⁻⁸). Equation (2) is thestandard free radical propagation reaction between a polymer of length iand a monomer M. The small free radical concentration ensured byequation (1) virtually eliminates termination reactions, and the halogenfunctionality is retained on polymers produced, which allows theproduction of copolymers from nearly any monomer amenable toconventional free radical polymerization.

The ATRP polymerization reaction starts with initiation. Initiation isaccomplished by adding an agent capable of decomposing to form freeradicals; the decomposed free radical fragment of the initiator attacksa monomer yielding a monomer-free radical, and ultimately produces anintermediate capable of propagating polymerization. These agents oftenare referred to as “initiators.” The initiation is typically based onthe reversible formation of growing radicals in a redox reaction betweenvarious transition metal compounds and an initiator.

Suitable initiators depend greatly on the details of the polymerization,including the types of monomers being used, the type of catalyst system,the solvent system and the reaction conditions. Simple organic halidesare typically used as model halogen atom transfer initiators. Exemplaryinitiators are aralkyl halides or aryl halides, such as benzyl bromideor benzyl chloride.

In ATRP, the introduction of a catalyst system to the reaction media isrequired to establish the equilibrium between active states (activepolymer free radicals for the growth of the polymer) and dormant states(the formed inert polymer). The catalyst is typically a transition metalcompound being capable of participating in a redox cycle with theinitiator and a dormant polymer chain. The transition-metal compoundused herein is a transition-metal halide. Any transition metal that canparticipate in a redox cycle with the initiator and dormant polymerchain, but does not form a direct C-metal bond with the polymer chain,is suitable in the present invention. The exemplary transition metalincludes Cu¹⁺, Cu²⁺, Fe²⁺, Fe³⁺, Ru²⁺, Ru³⁺, Ru⁴⁺, Ru⁵⁺, Ru⁶⁺, Cr²⁺,Cr³⁺, Mo⁰, Mo⁺, Mo²⁺, Mo³⁺, W²⁺, W³⁺, Mn³⁺, Mn⁴⁺, Rh⁺, Rh²⁺, Rh³⁺, Rh⁴⁺,Re²⁺, Re³⁺, Re⁴⁺, Co⁺, Co²⁺, Co³⁺, V²⁺, V³⁺, V⁴⁺, V⁵⁺, Zn⁺, Zn²⁺, Au⁺,Au²⁺, Au³⁺, Hg⁺, Hg²⁺, Pd⁰, Pd⁺, Pd²⁺, Pt⁰, Pt⁺, Pt²⁺, Pt³⁺, Pt⁴⁺, Ir⁰,Ir⁺, Ir²⁺, Ir³⁺, Ir⁴⁺, Os²⁺, Os³⁺, Os⁴⁺, Nb²⁺, Nb³⁺, Nb⁴⁺, Nb⁵⁺, Ta³⁺,Ta⁴⁺, Ta⁵⁺, Ni⁰, Ni⁺, Ni²⁺, Ni³⁺, Nd⁰, Nd⁺, Nd²⁺, Nd³⁺, Ag⁺, and Ag²⁺. Atypical transition-metal catalyst system used herein is CuCl/CuCl₂.

The ligand serves to coordinate with the transition metal compound suchthat direct bonds between the transition metal and growing polymerradicals are not formed, and the formed copolymer are isolated. Theligand can be any N-, O-, P- or S-containing compound that coordinateswith the transition metal to form a σ-bond, any C-containing compoundthat coordinates with the transition metal to form a π-bond, or anyC-containing compound that coordinates with the transition metal to forma C-transition metal σ-bond but does not form a C—C bond with themonomers under the polymerizing conditions. A typical ligand used hereinis pentamethyldiethylene-triamine (PMDETA).

The state of the art of ATRP has been reviewed by Matyjaszewski(Matyjaszewski et al., “Atom Transfer Radical Polymerization,” ChemicalReviews 101:2921-2990 (2001), which is hereby incorporated by referencein its entirety). More details for selection of initiators andcatalysts/ligand system for ATRP reaction can be found in U.S. Pat. No.5,763,548 to Matyjaszewski et al. and U.S. Pat. No. 6,538,091 toMatyjaszewski et al., which are hereby incorporated by reference intheir entirety. Detailed descriptions for ATRP polymerization of asimilar system, conjugated vegetable oil-based thermoplastic copolymer,can be found in U.S. patent application Ser. No. 13/744,733 to Cochranet al., which is hereby incorporated by reference in its entirety.

Thus, some embodiments of the present invention relates to a method ofmaking a thermoplastic copolymer or thermoplastic block copolymer viaATRP. The method comprises providing an acrylated polyol compositioncomprising plural acrylated polyol monomeric units having differentdegrees of acrylation of hydroxyl groups. The acrylated polyolcomposition has an average degree of acrylation greater than 1 and lessthan the number of the hydroxyl groups of the polyol. The method alsocomprises polymerizing the acrylated polyol composition through ATRP, inthe presence of a solvent, a catalyst, a counter catalyst, an initiator,and a ligand.

In some other embodiments, the present invention relates to a method ofmaking a thermoplastic block copolymer. The method comprises providingan acrylated polyol composition comprising plural acrylated polyolmonomeric units having different degrees of acrylation of hydroxylgroups. The acrylated polyol composition has an average degree ofacrylation greater than 1 and less than the number of the hydroxylgroups of the polyol. The method also comprises polymerizing theacrylated polyol composition through controlled radical polymerizationin the presence of a solvent, a catalyst, a counter catalyst, amacromolecular initiator, and a ligand to form the thermoplastic blockcopolymer. The method can further comprise the providing a radicallypolymerizable monomer different than the acrylated polyol monomericunit; and polymerizing the radically polymerizable monomer through atomtransfer radical polymerization (ATRP) with the formed thermoplasticblock copolymer as a macromolecular free radical initiator to add anadditional block to the thermoplastic block copolymer.

The formed thermoplastic block copolymer based on poly (acrylatedpolyol) can be used as a macromolecular free radical initiator to addadditional polymer block. Thus, the method can further compriseproviding a radically polymerizable monomer different than the acrylatedpolyol monomeric unit; and polymerizing the radically polymerizablemonomer with the formed thermoplastic block copolymer as amacromolecular free radical initiator to add an additional block to thethermoplastic block copolymer. The radically polymerizable monomersuitable for usage in the method are the same as the exemplaryembodiments for the monomer B, as described above in the thermoplasticblock copolymer.

One form of living free radical polymerization is RadicalAddition-Fragmentation Chain Transfer (RAFT). RadicalAddition-Fragmentation Chain Transfer (RAFT) polymerization is a type ofliving polymerization or controlled polymerization, utilizing a chaintransfer agent (CTA). Conventional RAFT polymerization mechanism,consisting of a sequence of addition-fragmentation equilibria, is shownin Moad et al., “Living Radical Polymerization by the Raft Process—aFirst Update,” Australian Journal of Chemistry 59: 669-92 (2006), whichis incorporated herein by reference in its entirety. The RAFTpolymerization reaction starts with initiation. Initiation isaccomplished by adding an agent capable of decomposing to form freeradicals; the decomposed free radical fragment of the initiator attacksa monomer yielding a propagating radical (P._(n)), in which additionalmonomers are added producing a growing polymer chain. In the propagationstep, the propagating radical (P._(n)) adds to a chain transfer agent(CTA), followed by the fragmentation of the intermediate radical forminga dormant polymer chain and a new radical (R.). This radical (R.) reactswith a new monomer molecule forming a new propagating radical (P._(m)).In the chain propagation step, (P._(n)) and (P._(m)) reach equilibriumand the dormant polymer chain provides an equal probability to allpolymers chains to grow at the same rate, allowing polymers to besynthesized with narrow polydispersity. Termination is limited in RAFT,and, if occurring, is negligible. Targeting a specific molecular weightin RAFT can be calculated by multiplying the ratio of monomer consumedto the concentration of CTA used by the molecular weight of the monomer.

The initiating agents often are referred to as “initiators.” Suitableinitiators depend greatly on the details of the polymerization,including the types of monomers being used, the type of catalyst system,the solvent system, and the reaction conditions. A typical radicalinitiator can be azo compounds, which provide a two-carbon centeredradical. Radical initiators such as benzoyl peroxide,azobisisobutyronitrile (AIBN), 1,1′ azobis(cyclohexanecarbonitrile) or(ABCN), or 4,4′-Azobis(4-cyanovaleric acid) (ACVA); redox initiator suchas benzoyl peroxide/N,N-dimethylaniline; microwave heating initiator;photoinitiator such as (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide;gamma radiation initiator; or lewis acids such as scandium(III) triflateor yttrium (III) triflate, are typically used in RAFT polymerization.

RAFT polymerization can use a wide variety of CTA agents. Suitable CTAagents should be capable of initiating the polymerization of themonomers (styrene and AESO) and achieve a narrow polydispersity in theprocess. For a RAFT polymerization to be efficient, the initial CTAagents and the polymer RAFT agent should have a reactive C═S doublebond; the intermediate radical should fragment rapidly without sidereactions; the intermediate should partition in favor of products, andthe expelled radicals (R.) should efficiently re-initiatepolymerization. Suitable CTA agent is typically a thiocarbonylthiocompound (ZC(═S)SR:

where R is free radical leaving group and Z is a group that modifiesaddition and fragmentation rates of RAFT polymerization. Exemplary CTAagents include, but are not limited to, a dithioester compound (whereZ=aryl, heteraryl, or alkyl), a trithiocarbonate compound (whereZ=alkylthio, arylthio, or heteroarylthio), a dithiocarbamate compound(where Z=arylamine or heterarylamine or alkylamine), and a xantatecompound (where Z=alkoxy, aryloxy, or heteroaryloxy), that are capableor reversible association with polymerizable free radicals. Z can alsobe sulfonyl, phosphonate, or phosphine. A more extensive list ofsuitable CTA agents (or RAFT agents) can be found in Moad et al.,“Living Radical Polymerization by the Raft Process—a First Update,”Australian Journal of Chemistry 59: 669-92 (2006); Moad et al., “LivingRadical Polymerization by the Raft Process—a Second Update,” AustralianJournal of Chemistry 62(11):1402-72 (2009); Moad et al., “Living RadicalPolymerization by the Raft Process—a Third Update,” Australian Journalof Chemistry 65: 985-1076 (2012); Skey et al., “Facile one pot synthesisof a range of reversible addition-fragmentation chain transfer (RAFT)agents.” Chemical Communications 35: 4183-85 (2008), which are herebyincorporated by reference in their entirety. Effectiveness of the CTAagent depends on the monomer being used and is determined by theproperties of the free radical leaving group R and the Z group. Thesegroups activate and deactivate the thiocarbonyl double bond of the RAFTagent and modify the stability of the intermediate radicals (Moad etal., “Living Radical Polymerization by the Raft Process—a SecondUpdate,” Australian Journal of Chemistry 62(11):1402-72 (2009), which ishereby incorporated by reference in its entirety). Typical CTA agentsused are 1-phenylethyl benzodithioate or 1-phenylethyl2-phenylpropanedithioate.

More details for selection of initiators, chain transfer agents, andother reaction conditions for RAFT reaction as well as detaileddescriptions for RAFT polymerization of a similar system, conjugatedvegetable oil-based thermoplastic copolymer, can be found in U.S.Provisional Application No. 61/825,241, filed May 20, 2013, to Cochranet al., which is hereby incorporated by reference in its entirety.

Thus, some embodiments of the present invention relates to a method ofmaking a thermoplastic copolymer or thermoplastic block copolymer viaRAFT. The method comprises providing an acrylated polyol compositioncomprising plurally acrylated polyol monomeric units having differentdegrees of acrylation of hydroxyl groups. The acrylated polyolcomposition has an average degree of acrylation greater than 1 and lessthan the number of the hydroxyl groups of the polyol. The method alsocomprises polymerizing the acrylated polyol composition through RAFT, inthe presence of a free radical initiator, a solvent, and a chaintransfer agent.

In one embodiment, polymerizing the acrylated polyol is carried out byRAFT polymerization. In RAFT polymerization, reaction time, temperature,and solvent concentration should be chosen appropriately to ensure theproduction of non-crosslinked thermoplastic elastomers. Reaction timerelates closely to the temperature the reaction is carried out at:higher temperature requires shorter reaction times and lower temperaturerequires longer reaction times. Monitoring the time of thepolymerization of the acrylated polyol is crucial as reacting theacrylated polyol too long causes the polymer to crosslink; whereasreacting the acrylated polyol for too short causes the polymerconversion to be too slow.

Temperatures for the RAFT polymerization on acrylated polyols can rangefrom room temperature to up to 180° C. Typical reaction temperatures fora RAFT reaction of acrylated polyol is 120° C. or lower, for instance,from 50 to 120° C., or from 50° C. to 85° C.

The monomeric acrylated polyol to CTA ratio can vary depending upon thedesired molecular weight. In polymerization of acrylated polyols, themultifunctional character of the monomer tends towards crosslinking.This crosslinking can be mitigated by the use of excess CTA. In oneembodiment, RAFT polymerization is carried out at a molar ratio of thechain transfer agent to the monomer ranging from 1:1 to 1:10000.

Solvent is selected based the requirements of acrylated polyolsolubility and a normal boiling point compatible with the polymerizationtemperature. The solvent used in the RAFT polymerization of acrylatedpolyol may be toluene, dioxane, THF, chloroform, cyclohexane, dimethylsulfoxide, dimethyl formamide, acetone, acetonitrile, n-butanol,n-pentanol, chlorobenzene, dichloromethane, diethylether, tert-butanol,1,2,-dichloroethylene, diisopropylether, ethanol, ethylacetate,ethylmethylketone, heptane, hexane, isopropylalcohol, isoamylalcohol,methanol, pentane, n-propylacohol, pentachloroethane,1,1,2,2,-tetrachloroethane, 1,1,1,-trichloroethane, tetrachloroethylene,tetrachloromethane, trichloroethylene, water, xylene, benzene,nitromethane, glycerol, or a mixture thereof. Typical solvent used forRAFT of acrylated polyols is methanol, glycerol, or a mixture thereof.

The concentrations of the monomeric acrylated polyol used in thereactions depend partially on the solubility of the monomer and thepolymer products as well as the evaporation temperature of the solvent.Solvent concentration can affect the gelation of the polymer.Insufficient solvent in the RAFT reaction can cause the polymer tocrosslink in a shorter time period without ever reaching high enoughconversions. Therefore, solvent is typically added in excess to allowthe polymer chains to grow and obtain a conversion rate to 80% withoutrisk of the polymer reaching the gel point. The concentration of themonomeric acrylated polyol dissolved in the solvent in the RAFTreactions may range from 5% to 100% weight percentage monomer.Typically, a monomer concentration of less than 90 wt % is suitable toensure the solubility of the resulting polymers and additionally toprevent premature gelation.

In one embodiment, the method is carried out in the presence of asolvent, with the acrylated polyol monomer having a concentration, whendissolved in the solvent, ranging from 1 wt % to 90 wt %, for instance,from 1 wt % to 40 wt %, from 1 wt % to 10 wt %, or from 20 wt % to 30 wt%.

In one embodiment, RAFT polymerization of the acrylated polyol iscarried out with a free radical initiator selected from the groupconsisting of benzoyl peroxide and azobisisobutyronitrile.

In one embodiment, RAFT polymerization of the acrylated polyol iscarried out in the presence of a chain transfer agent. The chaintransfer agent used can be a thiocarbonylthio compound, a dithioestercompound, a trithiocarbonate compound, a dithiocarbamate compound, or axanthate compound capable of reversible association with polymerizablefree radicals. Typically, the chain transfer agent is 1-phenylethylbenzodithioate, 1-phenyl ethyl 2-phenylpropanedithioate, or dibenzylcarbonotrithioate.

In some other embodiments, the present invention relates to a method ofmaking a thermoplastic block copolymer. The method comprises providingan acrylated polyol composition comprising plurally acrylated polyolmonomeric units having different degrees of acrylation of hydroxylgroups. The acrylated polyol composition has an average degree ofacrylation greater than 1 and less than the number of the hydroxylgroups of the polyol. The method also comprises polymerizing theacrylated polyol composition through controlled radical polymerizationin the presence of a free radical initiator, a solvent, and amacromolecular-chain transfer agent to form the thermoplastic blockcopolymer. The method can further comprise providing a radicallypolymerizable monomer different than the acrylated polyol monomericunit, and polymerizing the radically polymerizable monomer throughreversible addition-fragmentation chain-transfer polymerization (RAFT)with the formed thermoplastic block copolymer as a macromolecular-chaintransfer agent to add an additional block to the thermoplastic blockcopolymer.

The formed thermoplastic block copolymer based on poly (acrylatedpolyol) can be used as a macromolecular free radical initiator to addadditional polymer block. Thus, the method can further compriseproviding a radically polymerizable monomer different than the acrylatedpolyol monomeric unit; and polymerizing the radically polymerizablemonomer with the formed thermoplastic block copolymer as amacromolecular chain transfer agent to add an additional block to thethermoplastic block copolymer. The radically polymerizable monomersuitable for usage in the method are the same as the exemplaryembodiments for the monomer B, as described above in the thermoplasticblock copolymer.

Another aspect of the invention relates to a method of preparing athermoplastic statistical copolymer. The method comprises providingmonomer A, which is an acrylated polyol monomeric unit having differentdegrees of acrylation of hydroxyl groups, wherein the acrylated polyolmonomeric unit has an average degree of acrylation greater than 1 andless than the number of the hydroxyl groups of the polyol. The methodalso comprises providing a radically polymerizable monomer, representedby B. The method further comprises polymerizing monomer A and monomer Bsimultaneously, via reversible addition-fragmentation chain-transferpolymerization (RAFT), in the presence of a free radical initiator and achain transfer agent to form the thermoplastic statistical copolymer.The polymerizing step may be carried out under conditions effective toachieve a number average degree of polymerization (N_(n)) for thethermoplastic statistical copolymer of up to 100,000 without gelation.

The method can be used to simultaneously polymerize three or moredifferent monomer units. For instance, another radically polymerizablemonomer, represented by C can also be provided, in addition to monomer Aand monomer B. Monomer C is different than monomer A or monomer B.Monomer A, monomer B, and monomer C are then polymerized simultaneously,via RAFT, in the presence of the free radical initiator and the chaintransfer agent to form the thermoplastic statistical copolymer. Thepolymerizing step may be carried out under conditions effective toachieve a number average degree of polymerization (N_(n)) for thethermoplastic statistical copolymer of up to 100,000 without gelation.

Suitable RAFT polymerization conditions, reaction reagents, and monomersA, B, and C for the method of preparing the thermoplastic statisticalcopolymer are the same as those discussed in the above embodiments.

The above-described controlled radical polymerization can be used topolymerize acrylated polyol, under the above-described reactionconditions effective to produce the thermoplastic copolymer, blockcopolymer, and statistical copolymer with a molecular weight ranging 1KDa to 10 MKDa without gelation, for instance, a molecular weight of 50KDa to 200 KDa without gelation, or a molecular weight of 50 KDa to 10MKDa without gelation.

The thermoplastic copolymer, block copolymer, or statistical copolymercan be further reacted with an organic acid to esterify one or moreremaining un-acrylated hydroxy groups in one or more acrylated polyolmonomeric units, to change the solvent compatibility of thethermoplastic copolymer, block copolymer, or statistical copolymer.Alternatively, the acrylated polyol monomer, prior to polymerization,can be treated with the organic acid to esterify one or more remainingun-acrylated hydroxy groups the acrylated polyol monomer. Suitableorganic acid include any organic acid capable of converting the freehydroxy groups in the acrylated polyol into alkoxy groups, such asmethoxy or ethoxy. Typically used organic acids are formic acid, aceticacid, hexanoic acid, ethanoic acid, propanoic acid, amongst others.

The thermoplastic copolymer, block copolymer, or statistical copolymer,when containing unreacted acrylated groups, can undergo a crosslinkingreaction at an elevated temperature. Moreover, the thermoplasticcopolymer, block copolymer, or statistical copolymer can be furtherchemically modified with a crosslinking agent to undergo a crosslinkingreaction at an elevated temperature.

The crosslinking agent used to chemically modify the thermoplasticcopolymer, block copolymer, or statistical copolymer can include thosethat are typically used both in the synthesis of microgels and polymernetworks, e.g., degradable crosslinks such as an acetal linkage, ordisulfide linkages, resulting in the formation of degradable crosslinks.Exemplary crosslinking agents used to modify the thermoplasticcopolymer, block copolymer, and statistical copolymer includediethyleneglycol dimethacrylate (DEGDMA), diethylene glycol diacrylate,triethylene glycol dimethacrylate (TEGDMA), ethyleneglycoldimethacrylate (EGDMA), hexane-1,6-diol diacrylate (HDDA),methylene-bis-acrylamide (MBAm), divinylbenzene (DVB), p-divinylbenzene(p-DVB), sulfur, 1,4-cyclohexanedimethanol divinyl ether,N,N′-(1,2-dihydroxyethylene)bisacrylamide, ethylene glycol diacrylate,ethylene glycol dimethacrylate, 4,4′-Methylenebis(cyclohexylisocyanate), 1,4-Phenylenediacryloyl chloride, poly(ethylene glycol)diacrylate, poly(ethylene glycol) dimethacrylate, tetra(ethylene glycol)diacrylate, tetraethylene glycol dimethyl ether, triethylene glycoldimethacrylate, potassium metaborate, triethanolaminezirconate, sodiumtetraborate, boric acid, zirconium complexes, borate salts, methanol,etc.

The thermoplastic copolymer, block copolymer, or statistical copolymercan be further chemically modified with a reagent to confer an acidic orbasic functionality to the thermoplastic copolymer, block copolymer, orstatistical copolymer, making the thermoplastic copolymer, blockcopolymer, or statistical copolymer a pH adjusting agent. Unreactivehydroxyl groups in the polyols can be modified with a diacid such asoxalic acid, malonic acid, succinic acid, glutatic acid, adipic acid,pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid,dodecanoic acid; or a dicarboxylic acid such as ortho-phtalic acid,isophtalic acid, terephthalic acid, to provide an acidic environment.Unreactive hydroxyl groups in the polyols can also be modified with adibasic salt such as glyphosphate, hydroquinone, resorcinol, to providea basic environment.

The thermoplastic copolymer, block copolymer, or statistical copolymercan be further chemically modified with a reagent to confer a biocidicfunctionality to the thermoplastic copolymer, block copolymer, orstatistical copolymer, making the thermoplastic copolymer, blockcopolymer, or statistical copolymer a biocide agent. The reagent can bea quaternary ammonium, glutaraldehyde, tetrakis hydroxymethylphosphonium sulfate, etc.

Another aspect of the present invention relates to an asphaltcomposition. The asphalt composition comprises: i) an asphalt component;ii) a crumb rubber having a weight percentage in the range of 1% to 15%;and iii) a thermoplastic copolymer, block copolymer, or statisticalcopolymer as an asphalt additive, modifier, and/or filler having aweight percentage in the range of 0.01% to 1.05%. Any of thethermoplastic, block copolymer, and statistical copolymer discussed inthe above embodiments can be used herein.

A typical source of crumb rubber is ground tire rubber (GTR). Two basictypes of GTR are available based on the processes of preparing the GTR:cryogenic GTR is produced by shredding the tire into relatively largepieces and then subjecting the rubber to grinding under cryogenicconditions; ambient or warm-ground GTR is produced under warm or ambientgrinding procedure. The shredding and pulling apart of the tire rubberat ambient temperatures produces irregular particles having a highsurface area which desirably increases the number of reactive sitesavailable for bonding or cross-linking with the acrylated polyol-basedthermoplastic copolymer. There are many sources of GTR and the materialcan be used in the vulcanized or a devulcanized form. Devulcanized GTRproduced by either an oxidative or reductive process can be used.

GTR of various particle sizes can be incorporated into an asphaltcement. Typically, any GTR having particle sizes smaller than about 10mesh can be used. Exemplary ground tire rubbers have particle sizescapable of passing 20 mesh to 80 mesh screens, for instance, 30 mesh to40 mesh screens.

Another suitable source of crumb rubber is ground industrial wasterubber. These materials can be produced by either ambient grinding orcryogenic grinding. Different types of crumb rubbers can be mixed toachieve desired properties.

The aggregate used to prepare the asphalt component can be one or amixture of the various standard aggregates used in the art, includinggravel, crushed rock, stone, quarry gravel, and recycled pavingmaterial.

To enhance certain performance specifications, other asphalt modifiersor additives can be incorporated in the asphalt composition. Forinstance, mineral oil, heating oils, vegetable oils, or light petroleumdistillates can be added to an asphalt binder to maintain the PG valuewithin an acceptable range.

In the asphalt rubber formulations containing the poly(acrylatedpolyol)-based thermoplastic copolymer, block copolymer, or statisticalcopolymer, varying parameters, such as the concentration of thepoly(acrylated polyol)-based thermoplastic copolymer, block copolymer,or statistical copolymers, the average degree of acrylation in thepoly(aryclated polyol), and the molecular weight of the poly(aryclatedpolyol), can affect the performance of the resulting asphalt rubber.

For the poly(acrylated polyol)-based thermoplastic copolymer, typically,the thermoplastic copolymer, block copolymer, or statistical copolymercan have a weight percentage in the range of 0.1 wt % to 30 wt %relative to the weight of the crumb rubber, e.g., a range of 0.1 wt % to7 wt %, or 2.5 wt % to 6.5 wt % relative to the weight of the crumbrubber. The degree of acrylation for the poly(acrylated polyol)-basedthermoplastic copolymer typically can range from 1.001 to 2.9.Typically, a low degree of acrylation is desirable for the asphaltformulation, which ranges from 1.001 to 1.25, from 1.001 to 1.17, orfrom 1.001 to 1.05. The molecular weight for the poly(acrylatedpolyol)-based thermoplastic copolymer, block copolymer, or statisticalcopolymer can range from 1 KDa to 10M KDa, from 0 to 50 KDa, from 50 KDato 10M KDa, from 50 KDa to 200 KDa, or from 200 KDa to 10M KDa.Typically, a medium molecular weight of acrylated glycerol-basedthermoplastic copolymer, block copolymer, or statistical copolymer isdesirable for the asphalt formulation, which ranges from 200 KDa to 10MKDa.

The detailed formulations for the poly(acrylated polyol)-basedthermoplastic copolymer, block copolymer, or statistical copolymer interms of the average degree of acrylation in the poly(aryclated polyol),the molecular weight of the poly(aryclated polyol), and theconcentration of the poly(aryclated polyol) relative to the crumbrubber, and resulting performances of the asphalt rubbers areexemplified in Examples 3 and 4. The use of the poly(acrylated glycerol)in asphalt rubber improves performance in all the characteristics of theasphalt rubbers, e.g., reduces the low continue performance grade of theasphalt rubber, reduces sensitivity of the asphalt rubber's viscosity totemperature, reduces the asphalt rubber binder's modulus at lowtemperature, and lowers the separation of the asphalt rubbers aftercuring.

In one embodiment, the polyol in the poly(acrylated polyol)-basedthermoplastic copolymer, block copolymer, or statistical copolymer isglycerol; the average degree of acrylation ranges from 1.001 to 1.25;the thermoplastic copolymer, block copolymer, or statistical copolymerhas a molecular weight ranging from 50 KDa to 200 KDa; and the weightconcentration of the thermoplastic copolymer, block copolymer, orstatistical copolymer relative to the weight of the crumb rubber is4.5%. The resulting asphalt composition has one or more of the followingproperties: a high temperature grade higher than 78° C., a lowtemperature grade no higher than −29° C., a grade range higher than 107°C., a minimum mixing temperature lower than 171° C., and a minimumcompaction temperature lower than 161° C.

In one embodiment, the polyol in the poly(acrylated polyol)-basedthermoplastic copolymer, block copolymer, or statistical copolymer isglycerol; the average degree of acrylation ranges from 1.001 to 1.25;the thermoplastic copolymer, block copolymer, or statistical copolymerhas a molecular weight ranging from 50 KDa to 200 KDa; and the weightconcentration of the thermoplastic copolymer relative to the weight ofthe crumb rubber is 6.5%. The resulting asphalt composition has one ormore of the following properties: a high temperature grade higher than82° C., a low temperature grade no higher than −28.5° C., a grade rangehigher than 110° C., a minimum mixing temperature lower than 179° C.,and a minimum compaction temperature lower than 168° C.

The resulting asphalt composition prepared from the above embodimentscan be stable and homogenous for at least 3 days under a temperature of130° C. to 180° C.

Another aspect of the present invention relates to a method forpreparing a homogeneous asphalt composition. The method comprises mixinga thermoplastic copolymer, block copolymer, or statistical copolymer asan asphalt additive, modifier, and/or filler, with a weight percentagein the range of 0.01% to 1.05%, into an asphalt composition to form ahomogeneous asphalt composition. The asphalt composition comprises: i)an asphalt component, and ii) a crumb rubber having a weight percentagein the range of 1% to 15%. Any of the thermoplastic copolymer, blockcopolymer, or statistical copolymer discussed in the above embodimentscan be used herein.

Suitable crumb rubbers, sizes of the crumb rubbers, aggregate used toprepare the asphalt component, other asphalt modifiers or additives, anddetailed asphalt rubber formulations containing the poly(acrylatedpolyol) varying the average degree of acrylation, the molecular weightand the concentration of poly(aryclated polyol) have been described inthe above embodiments relating to the asphalt composition, and are alsosuitable for the method of preparing the homogeneous asphalt compositionherein.

One way to mix the thermoplastic copolymer, block copolymer, orstatistical copolymer into an asphalt composition is by premixing GTRand the thermoplastic copolymer, block copolymer, or statisticalcopolymer, then adding the pre-mixture to an asphalt component,typically a hot liquified asphalt cement, and continuing the mixing atthe same temperature range.

Alternatively, the GTR can be mixed with an asphalt component, typicallya hot liquified asphalt cement. The thermoplastic copolymer, blockcopolymer, or statistical copolymer is then added into the mixture, andthe mixing is continued at the same temperature range.

The mixing temperature can depend upon the qualities and characteristicsof the asphalt cement. The mixing of the acrylated-polyol-basedthermoplastic copolymer, block copolymer, or statistical copolymer withthe asphalt rubber composition is typically carried out at a temperaturerange of 130° C. to 180° C.

The use of the poly(acrylated glycerol) in an asphalt rubber lowersmixing and compaction temperatures and lowers the separation of theasphalt rubber after curing. Thus, the mixing can occur at a locationremote from the location at which the homogeneous asphalt composition isused. The resulting asphalt composition is stable and homogenous for atleast 3 days at a temperature of 130° C. to 180° C.

EXAMPLES

The following examples are for illustrative purposes only and are notintended to limit, in any way, the scope of the present invention.

Example 1—Synthesis of Poly(Acrylated Glycerol) (P(AG)) Via ReversibleAddition-Fragmentation Chain Transfer Polymerization (RAFT)

Acrylation of Glycerol

Glycerol was mixed with hydroquinone (inhibitor, 0.5 wt % of glycerol),thiamine pyrophosphate (TPP, catalyst) in a 0.06:1 mass ratio toglycerol, acrylic acid in a 1.5:1 mass ratio to glycerol, and DMSO in a1:1 mass ratio to glycerol. The reaction was stirred and bubbled for 20minutes, and then heated to 90° C. The reaction was allowed to proceedfor a minimum of 12 hours, and was ended by cooling to room temperature.The final acrylated glycerol was mixed with cyclohexane to remove DMSO,and was dried overnight on vacuum ovens under room temperature.

RAFT Polymerization of Acrylated Glycerol

RAFT synthesis was performed in a similar manner to the proceduredescribed in Moad et al., “Living radical polymerization by the raftprocess—a first update,” Australian Journal of Chemistry 59:669-92(2006); Moad et al., “Living radical polymerization by the raftprocess—a second update,” Australian Journal of Chemistry 62(11):1402-72(2009), which are hereby incorporated by reference in their entirety.Briefly, azobisisobutyronitrile (AIBN) was used as the initiator,1-phenylethyl benzodithioate (PBT) was used as the chain transfer agent(CTA).

Monomer (acrylated glycerol), initiator, CTA, and solvent (DMSO) weremixed under argon in a 100 mL round-bottomed flask with various massratios of monomer to solvent, 1:5 molar ratio of initiator to CTA, and10:1 molar ratio of monomer to CTA. The reaction flask was bubbled withargon for 30 minutes to remove oxygen from the system before thetemperature was increased. The reaction was run at 95° C., and thereaction time varied according the desired molecular weight (Mn). Thepolymer was precipitated by adding isopropanol drop wise, and was thendried on vacuum oven under room temperature for 24 hours.

Procedure for Calculating the Number of Acrylic Groups per Molecule

¹³C-NMR was used to calculate the number of acrylic groups per molecule.The integral of peak at ˜74 was set to a value of 1. The integral ofpeak at ˜64 would then be approximately 2. The integrals over both peaksat ˜130 were then combined. These are the carbon peaks of the acrylicgroups. The integral was then divided by two to obtain the averagenumber of acrylic groups per molecule because there are two carbons peracrylic group. The integral of peak at ˜168 was calculated (carboxylcarbon).

Varying ratios of reactants, the amount of solvent, and the reactiontime can vary the average number of acrylic groups per molecule. The¹³C-NMR results are shown in FIGS. 2A-2D. The correlation between theaverage number of acrylic groups per molecule and various reactionconditions are shown in Table 1. The results demonstrate that glycerol'sprimary alcohols were all acrylated, while not all the secondaryalcohols were acrylated. These findings agree with the reactivity ofalcohols (1°>2°>3°), suggesting that a longer reaction time, anincreased temperatures, or an increase in the acrylic acid concentrationare desirable to further acrylate the secondary alcohols.

TABLE 1 List of acrylated glycerol materials with their proper reactiontime, pH, and acrylic groups per molecule. 1 2 3 Glycerol (g) 50.31250.153 50.458 Acrylic Acid (mL) 55.35 55.35 117 Hydroquinone (g) 0.210.211 0.442 Triphenolphosphine (g) 2.617 2.616 2.616 DMSO (mL) 45 25 35Reaction Time 2.5 hr 3 hr 2.5 hr pH 7 7 7 Acrylic groups/molecule 0.850.91 2.15Viscoelastic/Thermal Characterization

Differential scanning calorimetry (DSC) experiments showed a glasstransition temperature (T_(g)) for the P(AG) at 14° C. See FIG. 3.

It was also found that the product's viscosity was affected by thedegree of acrylation—as the degree of acrylation increased the productbecame more viscous.

Rheology samples were mixed with butylated hydroxytoluene (BHT) toprevent crosslinking of the polymer. FIG. 4 shows the rheology curves oftwo different P(AG) polymers synthesized using two different CTA:2-ethylsulfanylthiocarbonylsulfanyl)-2-methylpropionic acid (EMP) andethyl 2-((ethoxycarbonothioyl)thio)-2-methylpropanoate (ETMP),respectively. The results showed a low modulus and liquid-like behaviorat high temperatures, which is the characteristics of thermoplasticelastomers. These curves also showed a rubbery plateau, signaling a highentangled system.

All these findings proved that these P(AG) polymers can be used assubstitutes for petroleum-based elastomers.

Example 2—Synthesis of Poly(Acrylated Glycerol) (P(AG)) orPoly(Acrylated Sorbitol) (P(AS)) Via RAFT

Synthesis of AG_(x) or AS_(x)

Synthesis of AG_(x) or AS_(x) can be carried out following the generalprocesses described below.

Process 1:

G moles glycerol (sorbitol) are combined with 1-5% by mass hydroquinoneor Ethanox 330™ (oxidative inhibitors), triphenylphosphine (TPP) orAmberlyst 15 (catalyst) in a 0.05:1 mass ratio to glycerol, and xG molof acrylic acid (x is the molar ratio of acrylic acid to glycerol orsorbitol). The mixture is stirred and air-sparged for 36 hours at either127° C. (TPP) or 120° C. (Amberlyst). Inhibitor and air-sparging (O₂)help to reduce auto-polymerization (which will otherwise lead togelation). After 36 hours, the reaction is terminated by cooling to roomtemperature. The monomer contains up to 20% of the initial charge ofacrylic acid.

Process 2:

G moles glycerol (sorbitol) are combined with 1-5% by mass hydroquinoneor Ethanox 330™, 0.05:1 mass ratio of triphenylphosphine (TPP) orAmberlyst 15 (catalyst) to glycerol, and xEG moles acrylic acid. Here,xE is the molar ratio of acrylic acid to glycerol or sorbitol, and meansan excess stoichiometric ratio that ranges from 1 to 3. The reaction isstirred and air-sparged for 8 hours between 90° C.-110° C.

In contrast to Process 1, the lower temperature in Process 2substantially reduces autopolymerization; the use of a molar excess ofacrylic acid allows the desired functionality to be achieved within theshortened time frame. After 8 hours, the reaction is quenched with a50%/50% water/acetone. The excess acrylic, water, and acetone are thenremoved under vacuum.

The characteristics of a representative set of poly(acrylated glycerol)P(AG)_(x) produced following the above processes are shown in Table 2.

TABLE 2 Representative table of acrylated polyols monomers. AG1.78AG1.42 AG1.08 AG1.02 Internal Sample Code gammf56 gammf41 gammf37gammf77 Process 2 2 1 1 Glycerol (g, mol) 100 1.09 1000 10.9 1250 13.6200 2.17 Acrylic Acid (g, mol) 174 2.4 1391 19.3 1304.2 18.1 208.7 2.9Hydroquinone (g, 7.83 0.071 0.57 0.07 58.7 0.53 10.4 0.095 mol) TPP (g,mol) — — — — — — 187.5 0.71 Amberlyst 15 (g) 5 50 Reaction Time 8 h 8 h24 h 36 h Acrylic 1.78 1.42 1.08 1.02 groups/molecule Residual Acrylic20 −20 −20 −20 Acid, w/wRAFT Polymerization of Acrylated Glycerol

RAFT polymerization was performed in a similar manner to the proceduredescribed in Moad et al., “Living radical polymerization by the raftprocess—a first update,” Australian Journal of Chemistry 59:669-92(2006); Moad et al., “Living radical polymerization by the raftprocess—a second update,” Australian Journal of Chemistry 62(11):1402-72(2009), which are hereby incorporated by reference in their entirety.Briefly, azobisisobutyronitrile (AIBN) was used as the initiator,dibenzylcarbonotrithioate (DBCT) as the chain transfer agent (CTA).

Monomer, initiator, CTA, and solvent (methanol and/or glycerol) weremixed under argon in a 100 mL round-bottomed flask with various massratios of monomer to solvent, 0.05 mass ratio of initiator to monomer,and various ratios of monomer to CTA, depending on the desired molecularweight of resulting polymer. The reaction flask was purged with argonfor 30 minutes to remove oxygen from the system before the temperaturewas increased. The reaction was conducted at 71° C., and the reactiontime was controlled to allow for maximum conversion withoutcross-linking the sample. The polymer was then precipitated by adding a50%/50% mixture of acetone and hexane. The solvent was then decanted,and acetone was mixed with the polymer to further clean the polymer.

The characteristics of a representative set of poly(acrylated glycerol)P(AG)_(x) produced in this manner are shown in Table 3.

TABLE 3 Characteristics P(AG) materials Material PAG1.08-L PAG1.02-MPAG1.08-H PAG1.42-L PAG1.42-M PAG1.78-L Polymer ghrmf30 ghrmf82 ghrmf37ghrmf54 ghrmf59 ghrmf59 Code Monomer gammf29 gammf77 gammf29 gammf41gammf41 gammf41 Code Monomer, 150 1.00 150 1.02 150 1.00 250 1.48 3001.78 100 0.53 (g|mol) CTA 4.35 15.0 0.44 1.50 0.044 0.15 7.25 24.96 0.873.00 2.9 9.98 (DBCTT), (g|mmol) AIBN 750 4.57 750 4.57 750 4.57 12507.61 1500 9.13 1500 9.13 (mg|mmol) [M]:[CTA] 67 680 6656 59 593 53Methanol, 55% 81% 81% 71% 88% 56% v/v % Time, h 4 8 8 8 8 8 Temperature,71 71 71 71 71 71 ° C. T_(g), ° C. −45 −34 −25 −30 −20 — [η], dL/g 0.130.17 0.17 0.09 0.14 —Procedure for Calculating the Conversion of Acrylic Acid to AcrylicGroups

Proton nuclear magnetic resonance was used to calculate the averagenumber of acrylic groups per molecule. The results are shown in FIG. 5.The integral of peak over 5.74-6.02 in deuterated DMSO was set to avalue of 1. The integral over both peaks at 5.74-5.82 were thencombined. The integral of peak at 5.90-6.02 was calculated. The peakbetween 5.74-5.82 measured the unreacted acrylic acid. The peak between5.90-6.02 measured the reacted acrylic groups. The integral over thereacted acrylic groups provide the conversion of acrylic acid to theacrylic groups in the polymer.

It was found that, to acrylate the secondary alcohols in the glycerol, ahigher acrylic acid concentration or an increased temperature wasneeded. These findings agree with the reactivity of alcohols (1°>2°>3°).

Molecular Characterization

DSC experiments showed glass transition temperature (T_(g)) for theP(AG) between −45° C. (sample ghrmf30) to −20° C. (sample ghrmf59). SeeTable 3. FIG. 6 shows an example of DSC results for the P(AG) (sampleghrmf82) demonstrating that the T_(g) was at −30° C.

It was also found that the product's viscosity was affected by thedegree of acrylation—as the degree of acrylation increased the productbecame more viscous.

Rheology samples were mixed with butylated hydroxytoluene (BHT) toprevent crosslinking of the polymer. FIG. 7 shows the rheology curves ofdistinct P(AG) polymers with different target molecular weights.

Example 3—Asphalt Rubber Modification with Polymers Derived from RAFTPolymerization of Acrylated Glycerol

The glycerol from the biodiesel industry was acrylated and polymerizedto different extents, and the resulting materials were then used in theproduction of asphalt rubber. The asphalt rubber binders “stabilized” bythe polymerized acrylated glycerol were tested, and the results werecompared to an asphalt rubber (GTR) without any stabilizer, and anasphalt rubber stabilized with Vestenamer®.

The performances of the asphalt rubber (AR) without any stabilizer,stabilized by the poly(acrylated glycerol), and stabilized byVestenamer® were compared in terms of rheology, viscosity, and themixing and compaction temperatures of the AR, the effect on theseparation during the AR storage, and the effect in the AR and residualAR.

Materials and Equipment

Poly(acrylated glycerol)(P(AG)) with different degrees of acrylation andpolymerization was prepared based on procedures similarly to theprocedures described in Example 1 or 2.

The base asphalt used was PG 58-28 (Seneca Petroleum), and the rubberwas ambient ground tire rubber (ambGTR) prepared by mechanical shreddingsupplied by Seneca Petroleum (030 mesh). Vestenamer® was used ascommercially available asphalt modifier to compare with the performanceof the P(AG) as the asphalt modifier.

a. Experiment 1

The asphalt and crumb rubber were blended at the following conditions:

-   -   Controlled velocity—3000 rpm    -   Controlled interaction temperature—180° C.    -   Interaction time—1 hour    -   Rubber concentration—15 wt % of the blended asphalt-rubber    -   Additives concentration—4.5 wt % of the rubber

The asphalt-rubber was then centrifuged at controlled velocity (1500rpm) at 180° C. for 3 minutes.

Three samples of AR were produced:

-   -   PG58-28+15 wt % ambGTR (referred to as control “AR”)    -   PG58-28+15 wt % (ambGTR+4.5% Vestenamer® by weight of ambGTR)        (referred to as “AR-V”)    -   PG58-28+15 wt % (ambGTR+4.5% Poly(Acrylated Glycerol) by weight        of ambGTR)—(referred to as “AR-AG”).

The samples were tested in the rotational viscometer (RV) tocharacterize their viscometry, in the dynamic shear rheometer (DSR)and/or bending beam rheometer (BBR) to characterize their rheology. Theseparation of the samples were tested by the cigar tube separation (CTS)method (ASTM D 7173). The binders were aged using the rolling thin filmoven (RTFO), to simulate short-term aging, and further aged using thepressurized aging vessel (PAV) to simulate long-term aging. The testingsconducted on AR binder samples and residual AR are shown in Table 4.

TABLE 4 The testings conducted on AR and residual AR Un-aged RTFO PAV ARRV, DSR, CT DSR DSR, BBR Residual AR RV, DSR DSR DSR, BBR (referred toas “Res”)

The viscosities results at various temperatures for the asphalt-rubberbinders and residual AR for the three samples are shown in FIGS. 8A-8C.

The rheology results measured by DSR for the AR binders and residual ARfor the three samples at various conditions (unaged, RTFO aged, and PAVaged) are shown in FIGS. 9A-9C.

The grading results for the AR binders and residual AR for the threesamples at various conditions (unaged, RTFO aged, and PAV aged) areshown in FIGS. 10A-10C.

The separation results for the AR binders (top and bottom, i.e., thebinder material in the top and bottom ⅓ of the cigar tube as specifiedin ASTM D 7173) for the three samples are shown in FIGS. 11A-11C.

All the testing results were analyzed and summarized in Tables 5-6.

TABLE 5 Low temperature grading summary PG low at −18° C. Stiffness(MPa) m-value AR Total 117 0.317 Residual 293 0.281 AR-V Total 136 0.302Residual 255 0.276 AR-AG Total 91.8 0.331 Residual 233 0.290

TABLE 6 ASTM D 7173 cigar tube separation test results. Total ResidualSeparation % Difference AR PG88-28 PG70-22 Top 82.3 1.7% (89.6-28)(72.7-22) Bottom 83.8 AR-V PG82-28 PG70-22 Top 82.7 3.6% (84.9-28)(73.4-22) Bottom 85.8 AR-AG PG76-28 PG70-22 Top 80.8 4.5% (78.3-28)(72.1-22) Bottom 84.5

b. Experiment 2

The experimental conditions were similar to the experimental conditionsin Experiment 1 in this example, except that the three samples of ARwere produced and cured (covered containers) in the oven at 163° C. for72 hours, and then centrifuged:

-   -   PG58-28+15% ambGTR (referred to as control “AR”)    -   PG58-28+15 wt % (ambGTR+4.5% Vestenamer® by weight of ambGTR)        (referred to as “AR-V”)    -   PG58-28+15 wt % (ambGTR+4.5% Poly(Acrylated Glycerol) by weight        of ambGTR)—(referred to as “AR-AG”).

The samples were tested in the dynamic shear rheometer (DSR) tocharacterize their rheology for total AR and residual materials. Theseparations of the samples were tested by CT for total AR and residualmaterials.

The viscosities results at various temperatures for the asphalt-rubberbinders and residual AR for the three samples are shown in FIGS.12A-12C.

The rheology results measured by DSR for the asphalt-rubber binders (topand bottom) for the three samples are shown in FIGS. 13A-13C.

The separation results for the asphalt-rubber binders for the threesamples are shown in FIGS. 14A-14C.

c. Comparison

Testing results for the three samples in Experiment 1 (unaged) andExperiment 2 (oven-cured) were compared. The results of comparison areshown in FIGS. 15A-15F, and summarized in Tables 7-9.

TABLE 7 Rubber swelling summary Rubber swelling Un-Aged Oven Cured %increase x weight % increase x weight 149.9% 2.50 234.7% 3.35 174.2%2.74 215.0% 3.15 223.7% 3.24 253.7% 3.54

TABLE 8 ASTM D 7173 cigar tube separation test results. GradingSeparation % Difference Total Residual Oven Cured Un-Aged 82 70 Top 82.22.3% 1.7% 82.9 72.7 Bottom 84.07 82 70 Top 82.18 2.0% 3.6% 83.2 74.4Bottom 83.82 82 70 Top 82.66 1.1% 4.5% 83.4 72.0 Bottom 83.60

TABLE 9 Viscosity - Mixing and Compaction Temperature (° C.) Un-AgedOven Cured Mix Compact Mix Compact AR Total 249.3* 227.6* 265.9* 244.4*Residual 164.2 151.4 177.5 163.1 AR-V Total 257.5* 236.0* 271.1* 248.0*Residual 164.2 151.4 181.1 166.9 AR-AG Total 287.6* 259.5* 265.9* 243.2*Residual 162.8 149.9 174.6 160.8 *The mixing and compacting temperaturesabove 180° C. were extrapolated

The results show that the rubber particles added in the asphalt affectedthe AR viscosity, which would have affected the accurate determinationof mixing and compaction temperatures.

Compared to the AR (control, without additives) and the AR withVestenamer®, the use of the poly(acrylated glycerol) in the AR improvedperformance in all the characteristics of the AR, i.e., reduced the lowcontinue performance grade of the AR, reduced sensitivity of the AR'sviscosity to temperature, reduced the AR binder's modulus at lowtemperature, and lowers the separation of the AR after curing (72 hoursat 163° C.).

Example 4—Asphalt Rubber Modification with Polymers Derived from RAFTPolymerization of Acrylated Glycerol

The glycerol from the biodiesel industry was acrylated and polymerizedto different extents, and the resulting materials were then used in theproduction of asphalt rubber. The AR binders “stabilized” by thepolymerized acrylated glycerol were tested, and the results werecompared to an asphalt rubber (GTR) without any stabilizer, an ARstabilized with Kraton® D1101, and an asphalt rubber stabilized withVestenamer®.

The overall performance of the AR stabilized by Vestenamer® was betterthan the control, unstabilized AR. However, the best performance wasattained by the AR stabilized by using 4.5 wt % of poly (acrylatedglycerol) with a low degree of acrylation and medium molecular weight(the weight percentage was relative to the weight of the rubber binder).

Materials and Equipment

Poly(acrylated glycerol)(P(AG)) with different degrees of acrylation andpolymerization was prepared based on procedures similarly to theprocedures described in Example 1 or 2.

The base asphalt used was PG 58-28 (Seneca Petroleum), and the rubberwas ambient ground tire rubber (ambGTR) prepared by mechanical shreddingsupplied by Seneca Petroleum (030 mesh). Kraton® D1101 and Vestenamer®were used as commercially available asphalt modifiers to compare withthe performance of the P(AG) as the AR modifier.

The following equipment was used to prepare AR binders, and tocharacterize modified AR.

-   -   Silverson shear mill    -   Binder Accelerated Separator—BAS (this method separates the        swelled rubber from the residual binder of the AR)    -   Rotational viscometer    -   Dynamic shear rheometer    -   Rolling thin film oven    -   Pressure aging vessel    -   Bending beam rheometer    -   Degassing oven        Experimental Procedures

Six samples of P(AG) with different degrees of acrylation andpolymerization were used in the production of the ARs at three differentconcentrations (2.5%, 4.5% and 6.5% by weight of the GTR) as summarizedin Table 10 below. Only 6.5% levels of concentration were used for the37 and 64 acrylated glycerol experimental blocks resulting in 14experimental compositions for the acrylated glycerol being evaluated.See Table 10. The Vestanamer® sample was blended at the same threeconcentrations with the GTR without any stabilizer and resulted in atotal of 18 experimental compositions being evaluated.

The polymer/GTR was added to the base asphalt at 12% by weight of thetotal AR binder.

TABLE 10 Tested materials for three degrees of acrylation andpolymerization (molecular weight) for different P(AG) contents MolecularWeight Low Re- Medium High AR sidual AR Residual AR Residual Degree ofLow 2.5% 78 82 Acylation 4.5% 6.5% 37 Medium 2.5% 54 59 4.5% 6.5% High2.5% 4.5% 6.5% 64

All samples were tested in the dynamic shear rheometer (DSR), bendingbeam rheometer (BBR) and in the rotational viscometer (RV) to obtaintheir high, inter-medium and low continuous grades. All the AR binderswere also tested for separation susceptibility (for 48 hours at 163°C.). The binders were aged using the rolling thin film oven (RTFO), tosimulate short term aging, and further aged using the pressurized agingvessel (PAV) to simulate long term aging. All the grading tests in thebinders were performed as specified in the Superpave®: Performancegraded asphalt binder specification and testing (2003) (AsphaltInstitute), as well as in AASHTO R 29-08 and AASHTO M 320-05. Thedetermination of the rheological properties of asphalt binder using adynamic shear rheometer was conducted according to ASTM D 7175-08.

Experimental Results

The results of each test are presented in a summary tables (FIGS.16-28), where the results of the AR stabilized with P(AG) were comparedwith the non-stabilized (control) AR, the AR stabilized withVestenamer®, and additionally a binder modified with 5% Kraton®.

The shaded cells in the summary tables regarding theVestenamer®-stabilized binders indicate the values that ideally can bereached or surpassed using the poly(acrylated glycerol)—these values arealso shaded in the summary tables regarding the P(AG)-stabilized bindersin dark grey. The light grey in the summary tables regarding theP(AG)-stabilized binders are the ones that have similar performance tothe Vestenamer®-stabilized binders, taking into account the testvariability.

a. High Temperature Continuous Grade for the Unaged Binders—DSR

The AR binders were unaged. The samples were tested in the DSR to obtaintheir high temperature continuous grades. The results for the unaged ARbinders modified by P(AG) are summarized in the table, and compared tothe results of a non-stabilized AR (control), AR binders stabilized withVestenamer®, and an asphalt binder modified with 5% Kraton®, as shown inFIG. 16.

The addition of rubber to the asphalt increased the high temperaturegrade of AR from 58° to 76°, and the high performance grade (PG) of theresidual binder was almost 70°. These results were further improved bythe addition of Vestenamer®, which behaved better than the asphaltmodified with 5%® Kraton D1101.

The PG of the stabilized AR binders, either with P(AG) or Vestenamer®,was always better than the non-stabilized AR (control). The addition ofthe poly(acrylated glycerol) improved the high PG of the binders to atleast the same extent as Vestenamer®, and in some cases (e.g. 6.5% AG82and 6.5% AG54) better than Vestenamer®_(.)

b. High Temperature Continuous Grade for the RTFO Aged Binders—DSR

The AR binders were aged using the RTFO to simulate short term aging.The samples were tested in the DSR to obtain their high temperaturecontinuous grades. The tests were performed according to ASTM D 2872-04.The results for the RTFO-aged AR binders modified by P(AG) aresummarized in the table, and compared to the results of a non-stabilizedAR (control), AR binders stabilized with Vestenamer®, and an asphaltbinder modified with 5% Kraton®, as shown in FIG. 17.

After the RTFO aging, all of the binders (except the 2.5 AG78) producedabout the same grade, which is the normal behavior for asphalt binders.The table in FIG. 18 summarized the mass loss percentage attained duringthe RTFO testing.

The RTFO aging process can result in variable results, and 1% mass lossis the acceptable criteria. Thus, the residuals of the AR stabilizedwith AG presented an acceptable value of mass loss (except the 6.5% ofthe AG 37, 59 and 64). The AR stabilized with 2.5% AG54 and 4.5% AG82performed better that the AR stabilized with Vestenamer®. The absolutevalues of the mass loss for the AR binder could not be measured becausethe bottles overflowed during the test.

c. Intermediate Temperature Continuous Grade for the RTFO+PAV AgedBinders—DSR

The AR binders were aged using the RTFO, and further aged using the PAVto simulate long term aging. The PAV aging was performed according toAASHTO R 28. The samples were tested in the DSR to obtain theirintermediate temperature continuous grades. The results for theRTFO+PAV-aged AR binders modified by P(AG) are summarized in the table,and compared to the results of a non-stabilized AR (control), AR bindersstabilized with Vestenamer®, and an asphalt binder modified with 5%Kraton®, as shown in FIG. 19.

For intermediate temperatures, the poorer behavior of the Kraton® D1101was noticeable when compared with the other binders, especially thenon-stabilizer AR (control). The Vestenamer® sample improved the ARbinder but had the opposite effect on the residual. The same trend wasobserved for the P(AG), but the improvements of the performance for theAR binder by using the P(AG) were more substantial than Vestenamer®.This more substantial improvements than the Vestenamer® sample by usingP(AG) were observed both for the AR binders and for the residual binder.

d. Low Temperature Continuous Grade for the RTFO+PAV Aged Binders—BBR

The AR binders were aged using the RTFO, and further aged using the PAVto simulate long term aging. The samples were tested in the BBR toobtain their low temperature continuous grades. The tests were performedaccording to ASTM D 6648-08. The results for the RTFO+PAV-aged ARbinders modified by P(AG) are summarized in the table, and compared tothe results of a non-stabilized AR (control), AR binders stabilized withVestenamer®, and an asphalt binder modified with 5% Kraton®, as shown inFIG. 20.

Similar to the results in the intermediate temperature continuousgrades, the Kraton® had the poorest performance in the low temperaturePG. The most significant result is that the stabilization of the ARbinders with P(AG) was very significant, even when compared with the ARbinders modified by the Vestenamer®.

e. Viscosity Determination for the Unaged Binders—RV

The viscosity testing was performed in the RV according to ASTM D4402-06. The results are illustrated in FIGS. 21A and 21B.

The viscosity test revealed the outstanding performance of the ARbinders stabilized with P(AG). These binders showed an improvedperformance with regard to the high, intermediate, and low temperaturegrades. Typically, it is expected that a relatively high level ofsensitivity to temperature would result. However, FIG. 21A shows mostlythe opposite, especially for the AR binder stabilized with 6.5% and 4.5%AG82 and 4.5% AG78. The addition of the Vestenamer® sample increased theviscosity of the AR binder when compared with the non-stabilized AR(control). By using the P(AG) to modify the AR, most binders presentedlower viscosities than the AR binders modified by Vestenamer®, and someAR binders modified by P(AG) showed an even lower viscosity than thecontrol AR.

The viscosities of the residual were also assessed for the AR bindersmodified with the P(AG), and a reduction of viscosity was observed whencompared to the AR, even to the Vestenamer® sample. However, thesensitivity to the temperature was quite similar among all the binders,which suggests that the P(AG) acts in conjunction with the rubberparticles. See FIG. 21B.

f. Storage Stability of the Asphalt Rubber Binders—DSR

The storage stability was tested in the DSR according to ASTM D 7173-05.The results of the percentage difference in DSR storage stability forthe AR binders modified by P(AG) are summarized in the table, andcompared to the results of a non-stabilized AR (control), AR bindersstabilized with Vestenamer®, and an asphalt binder modified with 5%Kraton®, as shown in FIG. 22.

The results showed that the Vestenamer® stabilized the AR binder. Thestorage stability of the AR binders modified by the P(AG) was improvedsignificantly for most of the tested samples compared to the control ARbinders.

g. Grade Range

The improvement of the high and low temperature grade is desirable andindicates in which conditions the binder can be used successfully. It isalso desirable to have a binder that can be used in a broad range ofclimate conditions. This is determined by the grade range.

The results of the grade range for the AR binders modified by P(AG) aresummarized in the table, and compared to the results of a non-stabilizedAR (control), AR binders stabilized with Vestenamer®, and an asphaltbinder modified with 5% Kraton®, as shown in FIG. 23.

Similar to the results in the intermediate and low temperaturecontinuous grades, the Kraton® D1101 showed the poorest performance inthe grade range. The addition of the GTR by itself enlarged the graderange by 16° C. After the AR was modified with Vestenamer®, an extra 6°C. was obtained. The best performance was obtained by the AR modified bythe P(AG), which reached a grade range of 113° C. (27° C. above theoriginal PG58-28 without the GTR, and 5° C. above the AR modified withVestenamer®).

h. Mixing and Compaction Temperatures

The mixing and compaction temperatures were determined as specified inSuperpave® Mix Design. Superpave Series No. 2 (SP-02) (AsphaltInstitute, Lexington, Ky. 2001). The results of the minimum mixingtemperatures and the minimum compaction temperatures for the AR bindersmodified by P(AG) are summarized in the tables, and compared to theresults of a non-stabilized AR (control), AR binders stabilized withVestenamer®, and an asphalt binder modified with 5% Kraton®, as shown inFIG. 24, and FIG. 25, respectively.

The viscosity of a material is very susceptible to the presence ofparticles; the particles increase dramatically the viscosity of thecomposite material, and this phenomenon is reflected in the mixingtemperature—a higher mixing temperature is needed to achieve the desiredviscosity for the composite material containing particles. This is wellillustrated in the tables in FIG. 24, and FIG. 25.

The control asphalt rubber presented the smallest increase in the mixingtemperature. The addition of the Vestenamer® sample increased the mixingtemperature by 6° C., but the Kraton® SBS-modified asphalt showed aneven higher increase of 7° C. However, the addition of the P(AG) onlyincreased the mixing temperature by 4° C. (e.g., using 4.5% AG82). SeeFIG. 24.

The performance of the P(AG) was excellent regarding the compactiontemperatures. The compaction temperatures of 6° C. lower than thecontrol AR were achieved by the AR modified with the P(AG). In fact, theoverall performance of the AR modified with the P(AG) in almost allconcentrations, degrees of acrylation, and molecular weights were betterthan the AR stabilized with the AR modified with Vestenamer® and theasphalt modified with the Kraton®. See FIG. 25.

i. Average Difference Between AR and Residual Viscosities

It is usually hard and time-consuming to determine if an asphalt binderis or is not stable during storage. Comparing the viscosities of the ARand residual binders, however, could provide an indication of thischaracteristic.

The average viscosity of the AR was compared with the residual,subtracting the latter from the former, and a smaller value of thedifference between the two indicates a more stable material. The resultsof the average difference between the AR and the residual viscositiesfor the AR binders modified by the P(AG) are summarized in the table,and compared to the results of a non-stabilized AR (control), AR bindersstabilized with Vestenamer®, and an asphalt binder modified with 5%Kraton®, as shown in FIG. 26.

The results show a remarkable similarity between the viscosities of theAR and residual binders of the materials stabilized with the P(AG).

Analysis and Discussion

Almost all the synthesized poly(acrylated glycerol) stabilizersperformed well in the three tested concentrations. To optimize theproduction process for the P(AG) and the AR binder formulationcontaining the P(AG), different tested parameters were categorized,analyzed, and ranked to assign relative weights to each parameter, asshown below:

Unaged high temperature PG 1.75 RTFO high temperature PG 0.75 RTFO massloss 0.50 Intermediate temperature PG 0.75 Low temperature PG 1.25 Graderange 1.50 viscosity 1.25 Minimum mixing temperature 1.00 Minimumcompaction temperature 1.00 Storage stability 2.00 (AR-Residual)viscosity difference 1.25

Before applying the relative weight, each parameter was converted in apercentage, in which the highest value was 100% and the lowest possiblevalue was −100%. In the first comparison, the values of the control ARwere set to be 0%. The final percentage rating of the AR bindersstabilized with the P(AG) and Vestenamer® were analyzed against thecontrol AR (non-stabilized), as shown in the table in FIG. 27.

Almost all the AR stabilized with the P(AG) and Vestenamer® performedbetter than the non-stabilized control AR. The highlighted cell in thetable shows the combination where the P(AG) performed best in theweighed ranking.

In the second comparison, the values of the AR modified with Vestenamer®were set to be 0%. The final percentage rating of the AR bindersstabilized with the P(AG) were analyzed against the AR modified withVestenamer®, as shown in the table in FIG. 28.

When compared to Vestemamer®, the P(AG) commonly showed betterperformance. The highlighted cell in the table shows the combinationwhere P(AG) performed best in the weighed ranking.

The AR binder modified by the P(AG) that overall showed a performance27% better than the AR binder modified by Vestenamer® was the P(AG) witha low degree of acrylation and a medium molecular weight (degree ofpolymerization), added at a 6.5% concentration by weight of the GTR (foran asphalt modified with 12 wt % ambient GTR).

The AR binder modified by the P(AG) with a low degree of acrylation anda medium molecular weight, added at a 4.5% concentration by weight ofthe GTR (for an asphalt modified with 12 wt % ambient GTR), showed anexceptional result—a performance 44% better than the control AR.

Example 5—Synthesis of Poly(Acrylated Glycerol)

Acrylation of Glycerol

Glycerol was mixed with phenothiazine or hydroquinone (inhibitor, 0.5 wt% of glycerol), Amberlyst 15 or thiamine pyrophosphate (TPP) as thecatalyst in a 0.06:1 mass ratio to glycerol, acrylic acid in a 1.5:1mass ratio to glycerol, and DMSO in a 1:1 mass ratio to glycerol. Thereaction was stirred and bubbled for 20 minutes, and then heated to 90°C. The reaction was allowed to proceed for a minimum of 12 hours, andwas ended by cooling to room temperature. The final acrylated glycerolwas mixed with cyclohexane to remove DMSO, and was dried overnight onvacuum ovens under room temperature.

Polymerization of Acrylated Glycerol

Polymerization of acrylated glycerol was performed in accordance withthe procedures as set forth in Example 1. The resulting threepoly(acrylated glycerol) polymers having molecular weights ranging from1 million Daltons to 10 thousand Daltons are shown in FIG. 30, with thegel permeation chromatography traces shown in FIG. 29.

Although preferred embodiments have been depicted and described indetail herein, it will be apparent to those skilled in the relevant artthat various modifications, additions, substitutions, and the like canbe made without departing from the spirit of the present invention andthese are therefore considered to be within the scope of the presentinvention as defined in the claims which follow.

What is claimed:
 1. A thermoplastic block copolymer comprising at leastone PA block and at least one PB block, wherein PA represents a polymerblock comprising one or more units of monomer A and PB represents apolymer block comprising one or more units of monomer B, with monomer Abeing an acrylated polyol monomeric unit having different degrees ofacrylation of hydroxyl groups, wherein the acrylated polyol monomericunit has an average degree of acrylation greater than 1 and less thanthe number of the hydroxyl groups of the polyol, and monomer B being aradically polymerizable monomer.
 2. The thermoplastic block copolymer ofclaim 1, wherein the PA block and PB block each have a linear orbranched-chain structure.
 3. The thermoplastic block copolymer of claim1, wherein the polyol of the monomer A is selected from the groupconsisting of ethylene glycol, propylene glycol, dipropylene glycol,1,2,4-butanetriol, 1,7-heptanediol, glycerol, panaxatriol, panaxytriol,talose, balsaminol B, momordol, erythritol, enterodiol, xylitol,miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol, aldohexose,aldopentose, aldotetrose, aldotriose, aldose, allose, altrose,arabinose, amylopectin, amylose, dextrose, erythrose, fructose,galactose, glucose, gulose, hexose, idose, ketohexose, ketose, lactose,lyxose, maltose, mannose, pentose, ribose, saccharose, sucrose, talose,tetrose, triose, xylose, amylopectin, and stereoisomers thereof.
 4. Thethermoplastic block copolymer of claim 1, wherein the polyol of themonomer A is glycerol.
 5. The thermoplastic block copolymer of claim 1,wherein the polyol of the monomer A is sorbitol.
 6. The thermoplasticblock copolymer of claim 1, wherein the polyol of the monomer A isdextrose.
 7. The thermoplastic block copolymer of claim 1, wherein oneor more acrylated polyol monomeric units of the PA block contain one ormore alkoxy groups derived from esterification of the un-acrylatedhydroxy groups.
 8. The thermoplastic block copolymer of claim 1, whereinthe monomer B is a vinyl, acrylic, diolefin, nitrile, dinitrile,acrylonitrile monomer, a monomer with reactive functionality, or acrosslinking monomer.
 9. The thermoplastic block copolymer of claim 1,wherein the monomer B is selected from the group consisting of styrene,α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene,vinyl pyridine, divinyl benzene, methyl acrylate, methyl (meth)acrylate,ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate,heptyl (meth)acrylate, hexyl (meth)acrylate, acrylonitrile,adiponitrile, methacrylonitrile, butadiene, isoprene, radicallypolymerizable plant oils, and mixtures thereof.
 10. The thermoplasticblock copolymer of claim 9, wherein the monomer B is radicallypolymerizable plant oil selected from the group consisting of soybeanoil, linseed oil, corn oil, flax seed oil, and rapeseed oil.
 11. Thethermoplastic block copolymer of claim 10 further comprising at leastone PC block, wherein PC represents a polymer block comprising one ormore units of monomer C, with monomer C being a radically polymerizablemonomer.
 12. The thermoplastic block copolymer of claim 1, wherein theblock copolymer has a molecular weight ranging from 5 to 10 MDa.
 13. Thethermoplastic block copolymer of claim 1, wherein the PA block has aglass transition temperature (Tg) below 0° C.